Non-lathering personal care composition in the form of an article

ABSTRACT

A non-lathering personal care article in the form of a porous dissolvable solid structure, comprising: from about 0% to about 10% ionic surfactant; from about 1% to about 60% of a non-surfactant cosmetic active; from about 15% to about 70% polymeric structurant, wherein the polymeric structurant has a weighted average molecular weight of from about 40,000 to about 500,000; and from about 1% to about 30% plasticizer. The article has a density of from about 0.03 g/cm3 to about 0.15 g/cm3.

CROSS REFERENCE TO RELATED APPLICATION

This application is a divisional of U.S. application Ser. No.12/424,812, filed Apr. 16, 2009, which claims the benefit of U.S.Provisional Application No. 61/045,444, filed Apr. 16, 2008.

FIELD OF THE INVENTION

The present invention relates to non-lathering personal carecompositions, especially those personal care compositions in the form ofan article that is a porous, dissolvable solid structure.

BACKGROUND OF THE INVENTION

The majority of personal care products in the market today are sold asliquid products. While widely used, liquid products have disadvantagesin terms of packaging, storage, transportation, and convenience of use.

Liquid personal care products typically are sold in bottles which addsignificant cost as well as packaging waste, much of which ends up inland-fills. Liquid personal care products also usually comprise asubstantial amount of water in the formula which adds significant weightand size translating into greater shipping and storage costs. Liquidpersonal care products can also be difficult to use in terms ofcontrolling dosage and the delivery of the product.

It is an object of the present invention to provide a non-latheringdissolvable solid personal care product that can be conveniently andquickly dissolved in the palm of the consumer to reconstitute a liquidproduct for ease of application to hair and/or skin while providingsufficient topical delivery of active agents for topical hair and/orskin applications. It is a further object of the present invention toprovide such a product that can be produced in an economical manner viaphysical aeration followed by drying.

Existing dissolvable personal care films comprise a water-solublepolymeric structurant and active ingredients. However, in order toachieve the requisite rapid dissolution rates needed for consumerconvenience, these films are generally on the order of less than 100microns thickness (typically 50 microns) and, thereby, are generally oftoo low a basis weight (typically 50-100 grams of solid per squaremeter) to enable consumer application of a sufficient dosage of activeingredients for entire body or whole head hair application andperformance, i.e., beyond lower dosage applications such as handcleansing and/or the facial applications.

In order to achieve sufficient dosage of raw materials within the palmof the consumer for whole head hair and whole body skin applications,relatively high basis weights are needed which requires objects with asubstantial third dimension (thickness) relative to thin films.Moreover, it has also been found that in order for these objects with asubstantial third dimension to quickly dissolve in the palm of theconsumer to reconstitute a liquid product for ease of application tohair/skin, they not only comprise a water-soluble polymeric structurantin combination with the active ingredients, but also are in the form ofa highly porous and predominantly open-celled (vs. closed-celled) solidstructure. It is believed that such water-soluble porous solidscomprising predominantly open-cells enable rapid water flux inside thestructure exposing a multiplicity of additional solid surface area forvastly increased dissolution rates. This is in contrast to water-solubleporous solids comprised of predominantly closed cells whereby the vastmajority of the interior cellular surfaces are not rapidly exposed tothe water upon wetting with dissolution progressing predominantly viasurface erosion and resulting in slower dissolution.

The production of such rapidly dissolvable open-celled porous solidstructures via physical aeration typically requires significantsurfactancy as a production means to generate the initial wet foam thatcan then be dried to the porous solid. For cleansing applications, i.e.,personal cleansing and hair shampoos, this is not a problem as thissurfactancy is also congruent with the desired cleansing productperformance (i.e., lathering). However, for non-cleansing applications,i.e., hair conditioning, styling, in-shower body lotions etc., thissurfactancy may be problematic as it can adversely affect the depositionof the intended hydrophobic actives to the hair and skin as well asgiving un-desirable in-usage signals of lathering/foaming/squeakiness tothe consumer that is not congruent with the intended care functions ofthese products (conditioning, coating, depositing, moisturizing, stylingetc.).

It is thus an object of the present invention to discover a means ofproduction of the porous solids via physical aeration (foaming), andalso enabling the formation of a predominantly open-celled foam forrapid dissolution, with minimal surfactancy such that the resultingrapidly dissolving porous solid is substantially non-lathering.

Freeze-drying aqueous solutions of water soluble polymeric structurantswith other actives is a known method of producing rapidly dispersing ordissolving porous solids with predominantly open cells via sublimationof water from the aqueous mixture leaving behind a skeleton of the driedpolymeric structurant. However, freeze-dried porous solids are typicallyvoid of plasticizing agents making them rigid and less desirable.Moreover, freeze-drying is an expensive process and less feasible foreconomical large scale production for personal care applications. Othertraditional dissolvable personal care products include porous solidsproduced by an anhydrous extrusion process and employing volatileblowing agents to produce the cellular structure via high pressure dropinduced expansion of the solid. However, this process is limited toanhydrous solid-sourced surfactants and ingredients which are limited innumber and make it more difficult to formulate a personal care productwith desired characteristics and performance. It would be highlydesirable to produce substantially non-lathering and rapid dissolvingporous solids with predominantly open-cells via physical aeration (highshear mechanical stirring or gas injection) and subsequent drying as amore commercially viable production method relative to freeze-drying.However, physical aeration essentially results in an air-in-water highinternal phase emulsion (a closed cell wet foam) which upon drying canlead to dried closed cell foam morphology wherein the air bubbles aretrapped/encased within the dried polymeric film lamellae or generallycollapses into a film in the instances where the foam is unstable.

It is therefore an object of the present invention to provide asubstantially non-lathering dissolvable open-celled porous solidpersonal care product that can be conveniently and quickly dissolved inthe palm of the consumer to reconstitute a liquid product for ease ofapplication to hair/skin while providing sufficient topical delivery ofactive agents for whole head hair and whole body skin applications (withsimilar performance as today's liquid products). It is a further objectof the present invention to provide such a product that can be producedby physical aeration followed by subsequent drying. It is an evenfurther object of the present invention to provide such a product withdesirable softness and flexibility.

SUMMARY OF THE INVENTION

A substantially non-lathering personal care article in the form of aporous dissolvable solid structure, comprising from about 0% to about10% ionic surfactant; from about 1% to about 60% of a non-surfactantcosmetic active; from about 15% to about 70% polymeric structurant,wherein the polymeric structurant has a weighted average molecularweight of from about 40,000 to about 500,000; and from about 1% to about30% plasticizer; wherein the article has a density of from about 0.03g/cm3 to about 0.15 g/cm3.

A pre-mix suitable for use in making a non-lathering personal carearticle that is in the form of a porous dissolvable solid structure,wherein said pre-mix has from about 15% to about 40% solids, has aviscosity of from about 2,500 cps to about 30,000 cps, and comprises (i)from about 0% to about 4% ionic surfactant; (ii) from about 0.3% toabout 20% of a non-surfactant cosmetic active; (iii) from about 5% toabout 25% polymeric structurant, and wherein the polymeric structuranthas a weighted average molecular weight of from about 40,000 to about500,000; and from about 0.3% to about 10% plasticizer.

A process for forming a non-lathering personal care article in the formof a porous dissolvable solid structure, wherein said process comprisesthe steps of: preparing a pre-mix comprising surfactant, dissolvedpolymer structurant, and optionally plasticizer, wherein said pre-mixhas: from about 15% to 40% total solids; and a viscosity of from about2,500 cps to 30,000 cps; aerating said pre-mix by introducing a gas intothe pre-mix to form a wet aerated pre-mix; forming the wet aeratedpre-mix into a desired one or more shapes to form shaped wet pre-mix;and drying the shaped wet pre-mix to a desired final moisture content,wherein the moisture content is from about 0.1% to about 15% moisture,to form the personal care article.

DETAILED DESCRIPTION OF THE INVENTION

In all embodiments of the present invention, all percentages are byweight of the total composition, unless specifically stated otherwise.All ratios are weight ratios, unless specifically stated otherwise. Allranges are inclusive and combinable. The number of significant digitsconveys neither a limitation on the indicated amounts nor on theaccuracy of the measurements. All numerical amounts are understood to bemodified by the word “about” unless otherwise specifically indicated.Unless otherwise indicated, all measurements are understood to be madeat 25° C. and at ambient conditions, where “ambient conditions” meansconditions under about one atmosphere of pressure and at about 50%relative humidity. All such weights as they pertain to listedingredients are based on the active level and do not include carriers orby-products that may be included in commercially available materials,unless otherwise specified.

Definitions

The term “porous solid” as used herein, unless otherwise specified,refers to a solid, interconnected, polymer-containing matrix thatdefines a network of spaces or cells that contain a gas, typically a gassuch as air. The present invention describes personal care compositionsin the form of open-celled porous dissolvable solid structures whereinthe spaces or cells are substantially interconnected.

As used herein, the terms “substantially non-lathering” and“non-lathering” are used interchangeably throughout to mean a lathervolume of from 0 ml to 20 ml.

“Personal care composition,” as used herein, means a composition thatmay be applied to mammalian keratinous tissue without undue undesirableeffects.

“Keratinous tissue,” as used herein, means keratin-containing layersdisposed as the outermost protective covering of mammals and includes,but is not limited to, skin, hair, scalp and nails.

The term “non-surfactant cosmetic active” or “cosmetic active” as usedherein, means one or a mixture of more than one non-surfactantmaterial(s) that, when applied to mammalian keratinous tissue, provide abenefit to the keratinous tissue. As used herein, the terms“non-surfactant cosmetic active” and “cosmetic active” are usedinterchangeably. The term “non-surfactant cosmetic active” is broadenough to include skin care actives, hair care actives, and beautybenefit agents, and may be used interchangeably with such termsthroughout the present application. Cosmetic actives may deliver beautybenefits such as, but not limited to, sebum inhibition, altering theappearance of skin and/or hair, reducing dryness, itchiness and/orflakiness, reducing skin pore size, exfoliation, desquamation, improvingthe appearance of the keratinous tissue, conditioning, moisturizing,smoothening, etc.

“Beauty benefit” or “benefit”, as used herein in reference to mammaliankeratinous tissue includes, but is not limited to cleansing, sebuminhibition, altering the appearance of skin and/or hair, reducingdryness, itchiness and/or flakiness, reducing skin pore size,exfoliation, desquamation, improving the appearance of the keratinoustissue, conditioning, moisturizing, smoothening, etc.

The present inventors have found that dissolvable solid personal careproducts can be prepared that can be conveniently and quickly dissolvedin the palm of the consumer to reconstitute a liquid product for ease ofapplication to hair and/or skin while providing sufficient topicaldelivery of active agents for whole head hair and whole body skinapplications (with similar performance as conventional liquid products).It has also been found that such products can be produced in aneconomical manner by physical aeration followed by subsequent drying.Additionally, it has been found that such products can now be producedwith desirable softness and flexibility and to be substantiallynon-lathering.

To meet the above mentioned objects of the present invention, it hasbeen found that a flexible personal care article in the form of a porousdissolvable solid structure can be made comprising ionic surfactant(from about 0% to about 10% anionic surfactant, in one embodiment fromabout 0% to about 6%, and in another embodiment from about 0% to about3%); a non-surfactant cosmetic active (from about 1% to about 60%cosmetic active, in one embodiment from about 5% to about 50%, and inanother embodiment from about 10% to about 40%); a polymer structurantcomprising one or more water-soluble polymers (from about 15% to about70 wt % polymer structurant, in one embodiment from about 22.5% to about60%, and in a another embodiment from about 30% to about 50%); and aplasticizer (from about 1% to about 30% plasticizer, in one embodimentfrom about 3% to about 24%, and in another embodiment from about 5% toabout 20%); and wherein the porous dissolvable solid structure has adensity of from about 0.03 g/cm³ to about 0.15 g/cm³, in one embodimentfrom about 0.04 g/cm³ to about 0.12 g/cm³, and in an alternateembodiment from about 0.06 g/cm³ to about 0.10 g/cm³.

In another embodiment, the personal care article has a basis weight offrom about 125 grams/m² to about 1,000 grams/m², in another embodimentfrom about 150 grams/m² to about 800 grams/m², in an alternateembodiment from about 200 grams/m² to about 700 grams/m², and in stillanother embodiment from about 300 grams/m² to about 650 grams/m²; and athickness as defined herein of from about 0.5 mm to about 10 mm, in oneembodiment from about 1 mm to about 7 mm, and in an alternate embodimentfrom about 2 mm to about 6 mm. In a further embodiment, the personalcare article is produced by the process comprising the steps ofpreparing a pre-mix comprising surfactant, dissolved polymerstructurant, and optionally plasticizer, wherein said pre-mix has: fromabout 15% to 40% total solids; and a viscosity of from about 2,500 cpsto 30,000 cps; and aerating said pre-mix by introducing a gas into thepre-mix to form a wet aerated pre-mix; and then forming the wet aeratedpre-mix into a desired one or more shapes to form shaped wet pre-mix;and then drying the shaped wet pre-mix to a desired final moisturecontent, wherein the moisture content is from about 0.1% to about 15%moisture, to form the personal care article.

According to yet another embodiment of the present invention, thepolymer structurant comprises one or more water-soluble polymers whereinat least one of the polymers has a weighted average molecular weight offrom about 40,000 to about 500,000, in another embodiment from about50,000 to about 400,000, in an alternate embodiment from about 60,000 toabout 300,000, and in still another embodiment from about 70,000 toabout 200,000.

In a particular embodiment, at least one of the one or morewater-soluble polymers is chosen such that a 2% by weight aqueoussolution of the water-soluble polymer gives a viscosity at 20° C. offrom about 4 centipoise to about 80 centipoise; in an alternateembodiment from about 5 centipoise to about 70 centipoise; and inanother embodiment from about 6 centipoise to about 60 centipoise.

In a another embodiment, the flexible personal care article in the formof a porous dissolvable solid structure, comprises in one embodimentfrom about 1% to about 50% of a nonionic surfactant, and in anotherembodiment from about 5% to about 45% nonionic surfactant, and inanother embodiment from about 10% to about 40% nonionic surfactant.

In another embodiment, the flexible personal care article in the form ofa porous dissolvable solid structure, comprises from about 1% to about50% of a polymeric surfactant, in another embodiment from about 5% toabout 45% polymeric surfactant, and in yet another embodiment from about10% to about 40% polymeric surfactant surfactant.

In the present invention the substantially non-lathering rapidlydissolving porous solids with a predominantly inter-connected,open-celled structure can be produced via physical aeration followed bysubsequent drying (as an alternative to conventional freeze drying).This can be accomplished by generating a physically aerated wet foamwith a controlled degree of foam instability during the drying processsuch that the thin film bubble facings drain into the plateau bordersconcurrent to drying/solidification resulting in a plurality of openchannels (“holes” and “struts”) and, particularly, without collapse ofthe foam structure during the drying process thereby maintaining thephysical strength and cohesiveness of the solid. Furthermore, it hasbeen found that this instability and coalescence could be controllablymanipulated such that the original closed-cell wet foam transformswithin the multi-hour drying process into a true open-celled porousstructure wherein the plurality of open channels extends to the solid'ssurface. Historically, when attempting to generate such products, theresults were stable wet foams drying to conventional closed-cell solidfoams or unstable wet foams drying to collapsed films. It was alsosurprising and non-intuitive to discover that the aeration to theinitial wet foam prior to drying (a lathering process) can surprisinglybe achieved in such a manner to produce the requisite open-celled porousstructure, but with the resulting rapidly dissolving article beingsubstantially non-lathering during consumer usage. This phenomenon hasbeen achieved by employing special surfactants and surfactantcombinations that enable lathering (foam generation) under the highenergy processing conditions employed during aeration to produce thestructure, but which are substantially non-lathering (little to no foamgeneration) under the lower energy consumer usage conditions when thesolids undergo dissolution. It has been discovered that these twocompeting performance requirements can be achieved by (i) minimizing thepresence of ionic surfactants, (ii) maximizing the presence of non-ionicsurfactants and/or polymeric surfactants, (iii) minimizing the overallsurfactant levels required for the aeration process, and (iv)combinations thereof.

It has been discovered that such substantially non-lathering open-celleddissolvable porous solids prepared by physical aeration followed bydrying can only be achieved within a narrowly defined rheological rangeas defined above. Achieving the relatively low viscosity range requiredis problematic due to the typically high polymeric structurant levelsrequired for solid integrity and cohesiveness as well as the desire forminimal water content (to minimize drying times and energy required forproduction). To achieve the required relatively low viscosity range ofthe present invention while producing integral and cohesive solidstructures, it has been discovered that several compositional strategiescan be employed, either alone or in combination, including but notlimited to: (i) employing water-soluble polymers within the requisitemolecular weight range but with relatively low viscosity build asdefined herein; (ii) dilution of the processing mixture with water;(iii) adding electrolyte or hydrotrope to manipulate the viscosity; (iv)adding non-ionic surfactants which achieve a rheology thinning effect,or (v) adding low molecular weight solvents to manipulate the viscosity.Importantly, aerating processing mixtures below the required viscosityrange results in less desirable, non-cohesive porous solids.

It has also been found that the above described characteristics of thepresent invention can be delivered by the production of open-celledporous structures employing either semi-continuous or continuousaeration equipment from the food industry that are used in themanufacture of marshmallows and dehydrated marshmallows.

I. COMPOSITION Non-Surfactant Cosmetic Actives

The dissolvable personal care articles of the present invention mayinclude any suitable cosmetic active. Such actives can include, but arenot limited to, conditioning agents for skin and hair, hair coloringagents, hair bleaching agents, hair styling agents, skin actives,perfumes, self-warming agents, anti-dandruff agents, hair dyes, shavinglotion actives, sunscreen actives, insect repellant actives, rash lotionactives, anti-acne actives, hair straightener actives, hair permingactives, anti-microbial actives, skin tanning actives, hair restoreractives, hair shine actives, skin make-up actives, and combinationsthereof. Furthermore, the article can comprise agents for stimulatinghair growth and/or promoting the appearance of fuller and/or thickerhair. Such materials can include, but are not limited to, minoxidil;cocktails of niacinamide, panthenol, and caffeine; and mixtures thereof.

A. Conditioning Agents

The dissolvable personal care solids of the present invention maycomprise an active agent comprising one or more conditioning agentssuitable for application to the hair. In a particular embodiment, theconditioning agents are selected from the group consisting of highmelting point fatty compounds, silicones, amido amines, acids, lowmelting point oils, waxes, cationic polymers, and cationic surfactants.The high melting fatty compound is incorporated in such a way and incombination with the other ingredients to provide a gel matrix which issuitable for providing various conditioning benefits such as slipperyand slick feel on wet hair, and softness, moisturized feel, and fly-awaycontrol on dry hair.

The high melting point fatty compound useful herein have a melting pointof 25° C. or higher, and is selected from the group consisting of fattyalcohols, fatty acids, fatty alcohol derivatives, fatty acidderivatives, and mixtures thereof. Non-limiting examples of the highmelting point compounds are found in International Cosmetic IngredientDictionary, Fifth Edition, 1993, and CTFA Cosmetic Ingredient Handbook,Second Edition, 1992.

The fatty alcohols useful herein are those having from about 14 to about30 carbon atoms, and in another embodiment from about 16 to about 22carbon atoms. These fatty alcohols are saturated and can be straight orbranched chain alcohols. Non-limiting examples of fatty alcoholsinclude, cetyl alcohol, stearyl alcohol, behenyl alcohol, and mixturesthereof.

The fatty acids useful herein are those having from about 10 to about 30carbon atoms, in one embodiment from about 12 to about 22 carbon atoms,and in another embodiment from about 16 to about 22 carbon atoms. Thesefatty acids are saturated and can be straight or branched chain acids.Also included are diacids, triacids, and other multiple acids which meetthe requirements herein. Also included herein are salts of these fattyacids. Non-limiting examples of fatty acids include lauric acid,palmitic acid, stearic acid, behenic acid, sebacic acid, and mixturesthereof.

The fatty alcohol derivatives and fatty acid derivatives useful hereininclude alkyl ethers of fatty alcohols, alkoxylated fatty alcohols,alkyl ethers of alkoxylated fatty alcohols, esters of fatty alcohols,fatty acid esters of compounds having esterifiable hydroxy groups,hydroxy-substituted fatty acids, and mixtures thereof. Non-limitingexamples of fatty alcohol derivatives and fatty acid derivatives includematerials such as methyl stearyl ether; the ceteth series of compoundssuch as ceteth-1 through ceteth-45, which are ethylene glycol ethers ofcetyl alcohol, wherein the numeric designation indicates the number ofethylene glycol moieties present; the steareth series of compounds suchas steareth-1 through 10, which are ethylene glycol ethers of stearethalcohol, wherein the numeric designation indicates the number ofethylene glycol moieties present; ceteareth 1 through ceteareth-10,which are the ethylene glycol ethers of ceteareth alcohol, i.e. amixture of fatty alcohols containing predominantly cetyl and stearylalcohol, wherein the numeric designation indicates the number ofethylene glycol moieties present; C₁-C₃₀ alkyl ethers of the ceteth,steareth, and ceteareth compounds just described; polyoxyethylene ethersof behenyl alcohol; ethyl stearate, cetyl stearate, cetyl palmitate,stearyl stearate, myristyl myristate, polyoxyethylene cetyl etherstearate, polyoxyethylene stearyl ether stearate, polyoxyethylene laurylether stearate, ethyleneglycol monostearate, polyoxyethylenemonostearate, polyoxyethylene distearate, propyleneglycol monostearate,propyleneglycol distearate, trimethylolpropane distearate, sorbitanstearate, polyglyceryl stearate, glyceryl monostearate, glyceryldistearate, glyceryl tristearate, and mixtures thereof.

High melting point fatty compounds of a single compound of high purityare useful herein. Single compounds of pure fatty alcohols can beselected from the group of pure cetyl alcohol, stearyl alcohol, andbehenyl alcohol. By “pure” herein, what is meant is that the compoundhas a purity of at least about 90%, and in another embodiment about 95%.These single compounds of high purity provide good rinsability from thehair when the consumer rinses off the composition.

Commercially available high melting point fatty compounds useful hereininclude: cetyl alcohol, stearyl alcohol, and behenyl alcohol havingtrade names KONOL series available from Shin Nihon Rika (Osaka, Japan),and NAA series available from NOF (Tokyo, Japan); pure behenyl alcoholhaving trade name 1-DOCOSANOL available from WAKO (Osaka, Japan),various fatty acids having trade names NEO-FAT available from Akzo(Chicago Ill., USA), HYSTRENE available from Witco Corp. (Dublin Ohio,USA), and DERMA available from Vevy (Genova, Italy).

The hair conditioning actives of the present invention may also comprisean amidoamine of the following general formula:R¹CONH(CH₂)_(m)N(R²)₂wherein R¹ is a residue of C₁₁ to C₂₄ fatty acids, R² is a C₁ to C₄alkyl, and m is an integer from 1 to 4.

The amidoamine, together with acids, can function as a cationicsurfactant in the composition of the present invention. It is believedthat; when used in the composition of the present invention, amidoaminecan provide improved deposition of silicones especially aminosilicones,compared to other cationic surfactants such as stearyl trimethylammonium chloride. It is also believed that; the composition of thepresent invention can provide improved conditioning benefits such assoftness and smoothness due to improved deposition of silicones. It isfurther believed that; the compositions of the present invention canprovide reduced frizziness in addition to softness and smoothness.

Amidoamine useful in the present invention includesstearamidopropyldimethylamine, stearamidopropyldiethylamine,stearamidoethyldiethylamine, stearamidoethyldimethylamine,palmitamidopropyldimethylamine, palmitamidopropyldiethylamine,palmitamidoethyldiethylamine, palmitamidoethyldimethylamine,behenamidopropyldimethylamine, behenamidopropyldiethylamine,behenamidoethyldiethylamine, behenamidoethyldimethylamine,arachidamidopropyldimethylamine, arachidamidopropyldiethylamine,arachidamidoethyldiethylamine, arachidamidoethyldimethylamine, andmixtures thereof; and in another embodimentstearamidopropyldimethylamine, stearamidoethyldiethylamine, and mixturesthereof.

Commercially available amidoamines useful herein include:stearamidopropyldimethylamine having tradename SAPDMA available formInolex, and tradename Amidoamine MPS available from Nikko, andbehenamidopropyl dimethylamine having a tradename IncromineBB availablefrom Croda. Without being limited to the theory, it is believed thatbehenamidopropyl dimethylamine provides improved tolerance to the hairfor humidity in the surrounded circumstance compared to otheramidoamines having shorter alkyl chain. It is believed thatbehenamidopropyl dimethylamine provides reduced frizziness and/orfly-away in rainy day and/or humid day.

The hair conditioning actives of the present invention may comprise anacid selected from the group consisting of L-glutamic acid, lactic acid,hydrochloric acid, malic acid, succinic acid, acetic acid, fumaric acid,L-glutamic acid hydrochloride, tartaric acid, citric acid, and mixturesthereof; in another embodiment L-glutamic acid, lactic acid, citricacid, and mixtures thereof. The mole ratio of amidoamine to acid can bein one embodiment from about 1:0.3 to about 1:1.3, and in anotherembodiment from about 1:0.5 to about 1:1.0.

The hair conditioning actives of the present invention may comprise oneor more silicones including high molecular weight polyalkyl or polyarylsiloxanes and silicone gums; lower molecular weight polydimethylsiloxane fluids; and aminosilicones.

In one embodiment the high molecular weight polyalkyl or polyarylsiloxanes and silicone gums have a viscosity of from about 100,000 mPa·sto about 30,000,000 mPa·s at 25° C. in another embodiment from about200,000 mPa·s to about 30,000,000 mPa·s and in on embodiment a molecularweight of from about 100,000 to about 1,000,000, and in anotherembodiment from about 120,000 to about 1,000,000.

Higher molecular weight silicone compounds useful herein includepolyalkyl or polyaryl siloxanes with the following structure:

wherein R⁹³ is alkyl or aryl, and p is an integer from about 1,300 toabout 15,000, and in another embodiment from about 1,600 to about15,000. Z⁸ represents groups which block the ends of the siliconechains. The alkyl or aryl groups substituted on the siloxane chain (R⁹³)or at the ends of the siloxane chains Z⁸ can have any structure as longas the resulting silicone remains fluid at room temperature, isdispersible, is neither irritating, toxic nor otherwise harmful whenapplied to the hair, is compatible with the other components of thecomposition, is chemically stable under normal use and storageconditions, and is capable of being deposited on and conditions thehair. Suitable Z⁸ groups include hydroxy, methyl, methoxy, ethoxy,propoxy, and aryloxy. The two R⁹³ groups on the silicon atom mayrepresent the same group or different groups. In one embodiment, the twoR⁹³ groups represent the same group. Suitable R⁹³ groups include methyl,ethyl, propyl, phenyl, methylphenyl and phenylmethyl. In one embodimentthe silicone compounds are polydimethylsiloxane, polydiethylsiloxane,and polymethylphenylsiloxane. Polydimethylsiloxane, which is also knownas dimethicone. Commercially available these silicone compounds usefulherein include, for example, those available from the General ElectricCompany in their TSF451 series, and those available from Dow Corning intheir Dow Corning SH200 series.

The silicone compounds that can be used herein also include a siliconegum. The term “silicone gum”, as used herein, means a polyorganosiloxanematerial having a viscosity at 25° C. of greater than or equal to1,000,000 mPa·s. It is recognized that the silicone gums describedherein can also have some overlap with the above-disclosed siliconecompounds. This overlap is not intended as a limitation on any of thesematerials. The “silicone gums” will typically have a mass molecularweight in excess of about 165,000, generally between about 165,000 andabout 1,000,000. Specific examples include polydimethylsiloxane,poly(dimethylsiloxane methylvinylsiloxane) copolymer,poly(dimethylsiloxane diphenylsiloxane methylvinylsiloxane) copolymerand mixtures thereof. Commercially available silicone gums useful hereininclude, for example, TSE200A available from the General ElectricCompany.

In one embodiment the lower molecular weight silicones have a viscosityof from about 1 mPa·s to about 10,000 mPa·s at 25° C., in anotherembodiment from about 5 mPa·s to about 5,000 mPa·s and in one embodimenta molecular weight of from about 400 to about 65,000, and in anotherembodiment from about 800 to about 50,000.

Lower molecular weight silicone compounds useful herein includepolyalkyl or polyaryl siloxanes with the following structure:

wherein R⁹³ is alkyl or aryl, and p is an integer from about 7 to about850, and in another embodiment from about 7 to about 665. Z⁸ representsgroups which block the ends of the silicone chains. The alkyl or arylgroups substituted on the siloxane chain (R⁹³) or at the ends of thesiloxane chains Z⁸ can have any structure as long as the resultingsilicone remains fluid at room temperature, is dispersible, is neitherirritating, toxic nor otherwise harmful when applied to the hair, iscompatible with the other components of the composition, is chemicallystable under normal use and storage conditions, and is capable of beingdeposited on and conditions the hair. Suitable Z⁸ groups includehydroxy, methyl, methoxy, ethoxy, propoxy, and aryloxy. The two R⁹³groups on the silicon atom may represent the same group or differentgroups. In one embodiment the two R⁹³ groups represent the same group.Suitable R⁹³ groups include methyl, ethyl, propyl, phenyl, methylphenyland phenylmethyl. The silicone compounds useful herein includepolydimethylsiloxane, polydiethylsiloxane, and polymethylphenylsiloxane.In one embodiment the silicone is polydimethylsiloxane, which is alsoknown as dimethicone. Commercially available these silicone compoundsuseful herein include, for example, those available from the GeneralElectric Company in their TSF451 series, and those available from DowCorning in their Dow Corning SH200 series.

In one embodiment, the active agent of the present invention includesone or more aminosilicones. Aminosilicones, as provided herein, aresilicones containing at least one primary amine, secondary amine,tertiary amine, or a quaternary ammonium group. In one embodiment theaminosilicones may have less than about 0.5% nitrogen by weight of theaminosilicone, in another embodiment less than about 0.2%, in yetanother embodiment, less than about 0.1%. Higher levels of nitrogen(amine functional groups) in the amino silicone tend to result in lessfriction reduction, and consequently less conditioning benefit from theaminosilicone. It should be understood that in some product forms,higher levels of nitrogen are acceptable in accordance with the presentinvention.

In one embodiment, the aminosilicones used in the present invention havea particle size of less than about 50μ once incorporated into the finalcomposition. The particle size measurement is taken from disperseddroplets in the final composition. Particle size may be measured bymeans of a laser light scattering technique, using a Horiba model LA-910Laser Scattering Particle Size Distribution Analyzer (HoribaInstruments, Inc.).

In one of the embodiments, the aminosilicone has a viscosity of fromabout 1,000 cs (centistokes) to about 1,000,000 cs, in anotherembodiment from about 10,000 cs to about 700,000 cs, in yet anotherembodiment from about 50,000 cs to about 500,000 cs, and in yet anotherembodiment from about 100,000 cs to about 400,000 cs. This embodimentmay also comprise a low viscosity fluid, such as, for example, thosematerials described below in Section F.(1). The viscosity ofaminosilicones discussed herein is measured at 25° C.

In another embodiment, the aminosilicone has a viscosity of from about1,000 cs to about 100,000 cs, in another embodiment from about 2,000 csto about 50,000 cs, in another embodiment from about 4,000 cs to about40,000 cs, and in yet another embodiment from about 6,000 cs to about30,000 cs.

The aminosilicone can be contained in the composition of the presentinvention at a level by weight of from about 0.05% to about 20% in oneembodiment, from about 0.1% to about 10% in another embodiment, and fromabout 0.3% to about 5% in yet another embodiment.

Examples of aminosilicones for use in embodiments of the subjectinvention include, but are not limited to, those which conform to thegeneral formula (I):(R¹)_(a)G_(3−a)—Si—(—OSiG₂)_(n)—(—OSiG_(b)(R¹)_(2−b))_(m)—O—SiG_(3−a)(R¹)_(a)  (I)wherein G is hydrogen, phenyl, hydroxy, or C₁-C₈ alkyl, and in oneembodiment methyl; a is 0 or an integer having a value from 1 to 3, andin one embodiment is 1; b is 0, 1, or 2, and in one embodiment is 1;wherein when a is 0, b is not 2; n is a number from 0 to 1,999; m is aninteger from 0 to 1,999; the sum of n and m is a number from 1 to 2,000;a and m are not both 0; R¹ is a monovalent radical conforming to thegeneral formula C_(q)H_(2q)L, wherein q is an integer having a valuefrom 2 to 8 and L is selected from the following groups:—N(R²)CH₂—CH₂—N(R²)₂; —N(R²)₂; —N(R²)⁺ ₃A⁻; —N(R²)CH₂—CH₂—NR²H₂A⁻;wherein R² is hydrogen, phenyl, benzyl, or a saturated hydrocarbonradical, and in one embodiment is an alkyl radical from about C₁ toabout C₂₀; A⁻ is a halide ion.

Some silicones for use herein can include those aminosilicones thatcorrespond to formula (I) wherein m=0, a=1, q=3, G=methyl, n is in oneembodiment from about 1500 to about 1700, in another embodiment is about1600; and L is —N(CH₃)₂ or —NH₂, and in one embodiment is —NH₂. Otheraminosilicones can include those corresponding to formula (I) whereinm=0, a=1, q=3, G=methyl, n is in one embodiment from about 400 to about600, in another embodiment is about 500; and L is —N(CH₃)₂ or —NH₂, inyet another embodiment is —NH₂. These aminosilicones can be called asterminal aminosilicones, as one or both ends of the silicone chain areterminated by nitrogen containing group.

An exemplary aminosilicone corresponding to formula (I) is the polymerknown as “trimethylsilylamodimethicone”, which is shown below in formula(II):

wherein n is a number from 1 to 1,999 and m is a number from 1 to 1,999.

The active agent of the present invention may also include low meltingpoint oils having a melting point of less than 25° C. The low meltingpoint oil useful herein is selected from the group consisting of:hydrocarbon having from 10 to about 40 carbon atoms; unsaturated fattyalcohols having from about 10 to about 30 carbon atoms such as oleylalcohol; unsaturated fatty acids having from about 10 to about 30 carbonatoms; fatty acid derivatives; fatty alcohol derivatives; ester oilssuch as pentaerythritol ester oils, trimethylol ester oils, citrateester oils, and glyceryl ester oils; poly α-olefin oils; and mixturesthereof. Low melting point oils useful herein are selected from thegroup consisting of: ester oils such as pentaerythritol ester oils,trimethylol ester oils, citrate ester oils, and glyceryl ester oils;poly α-olefin oils; and mixtures thereof,

Particularly useful pentaerythritol ester oils and trimethylol esteroils herein include pentaerythritol tetraisostearate, pentaerythritoltetraoleate, trimethylolpropane triisostearate, trimethylolpropanetrioleate, and mixtures thereof. Such compounds are available from KokyoAlcohol with tradenames KAKPTI, KAKTTI, and Shin-nihon Rika withtradenames PTO, ENUJERUBU TP3SO.

Particularly useful citrate ester oils herein include triisocetylcitrate with tradename CITMOL 316 available from Bernel, triisostearylcitrate with tradename PELEMOL TISC available from Phoenix, andtrioctyldodecyl citrate with tradename CITMOL 320 available from Bernel.

Particularly useful glyceryl ester oils herein include triisostearinwith tradename SUN ESPOL G-318 available from Taiyo Kagaku, trioleinwith tradename CITHROL GTO available from Croda Surfactants Ltd.,trilinolein with tradename EFADERMA-F available from Vevy, or tradenameEFA-GLYCERIDES from Brooks.

Particularly useful poly α-olefin oils herein include polydecenes withtradenames PURESYN 6 having a number average molecular weight of about500 and PURESYN 100 having a number average molecular weight of about3000 and PURESYN 300 having a number average molecular weight of about6000 available from Exxon Mobil Co.

Cationic polymers useful herein are those having an average molecularweight of at least about 5,000, typically from about 10,000 to about 10million, and in one embodiment are from about 100,000 to about 2million.

Suitable cationic polymers include, for example, copolymers of vinylmonomers having cationic amine or quaternary ammonium functionalitieswith water soluble spacer monomers such as acrylamide, methacrylamide,alkyl and dialkyl acrylamides, alkyl and dialkyl methacrylamides, alkylacrylate, alkyl methacrylate, vinyl caprolactone, and vinyl pyrrolidone.Other suitable spacer monomers include vinyl esters, vinyl alcohol (madeby hydrolysis of polyvinyl acetate), maleic anhydride, propylene glycol,and ethylene glycol. Other suitable cationic polymers useful hereininclude, for example, cationic celluloses, cationic starches, cassia andcationic guar gums.

Suitable cationic surfactants include, for example, stearyl trimethylammonium chloride, cetyl trimethyl ammonium chloride, behenyl trimethylammonium chloride, and distearyl dimethyl ammonium chloride.

Other suitable cationic surfactants can include asymmetric dialkylquaternized ammonium salt cationic surfactant. The asymmetric dialkylquaternized ammonium salt cationic surfactant can be included in thecomposition at a level by weight of in one embodiment from about 0.1% toabout 10%, in another embodiment from about 0.2% to about 5%, in yetanother embodiment from about 0.4% to about 3% in view of balancebetween ease-to-rinse feel and wet conditioning benefits. The use ofhigher level of asymmetric dialkyl quaternized ammonium salt tends tolead to reduced wet conditioning benefits such as reduced slippery feel,while the use of lower level of asymmetric dialkyl quaternized ammoniumsalt tends to lead to reduced ease-to-rinse feel.

Some of the asymmetric dialkyl quaternized ammonium salt cationicsurfactants useful herein are those having the formula (I):

wherein R⁷¹ is selected from an alkyl group of from 12 to 30 carbonatoms or an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl,aryl or alkylaryl group having up to about 30 carbon atoms; R⁷² isselected from an alkyl group of from 5 to 12 carbon atoms or anaromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl oralkylaryl group having up to about 12 carbon atoms; R⁷³ and R⁷⁴ areindependently selected from an alkyl group of from 1 to about 4 carbonatoms or an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl,aryl or alkylaryl group having up to about 4 carbon atoms; and X⁻ is asalt-forming anion such as those selected from halogen, (e.g. chloride,bromide), acetate, citrate, lactate, glycolate, phosphate, nitrate,sulfonate, sulfate, alkylsulfate, and alkyl sulfonate radicals. Thealkyl groups can contain, in addition to carbon and hydrogen atoms,ether linkages, and other groups such as amino groups. The longer chainalkyl groups, e.g., those of about 12 carbons, or higher, can besaturated or unsaturated and/or straight or branched. In one embodiment,R⁷¹ is selected from a non-functionalized alkyl group of from 12 to 30carbon atoms, in another embodiment from 16 to 22 carbon atoms, in yetanother embodiment 18 to 22 carbon atoms, and in yet another embodiment18 carbon atoms; R⁷² is selected from a non-functionalized alkyl groupof in one embodiment from 5 to 12 carbon atoms, in another embodimentfrom 6 to 10 carbon atoms, in another embodiment 8 carbon atoms; R⁷³ andR⁷⁴ are independently selected from CH₃, C₂H₅, C₂H₄OH, and mixturesthereof; and X is selected from the group consisting of Cl, Br, CH₃OSO₃,C₂H₅OSO₃, and mixtures thereof. In one embodiment, R⁷¹ is a straight,saturated non-functionalized alkyl group, and R⁷² is a branchedsaturated non-functionalized alkyl group. In another embodiment, thebranched group of R⁷² is a straight, saturated alkyl group of from 1 to4 carbon atoms, and in yet another embodiment 2 carbon atoms.

The above asymmetric dialkyl quaternized ammonium salt cationicsurfactants provide improved ease-to-rinse feel compared to mono-alkylquaternized ammonium salt cationic surfactants such as behenyl trimethylammonium salts and symmetric dialkyl quaternized ammonium cationicsurfactants such as distearyl dimethyl ammonium salts, while stillmaintaining balanced wet conditioning benefits like slippery feel. Ithas been further found that among the above asymmetric dialkylquaternized ammonium salt cationic surfactants, those having a longerstraight saturated alkyl group and a shorter branched alkyl group,together with two more C1-4 alkyl groups, provide improved balancebetween ease-to-rinse feel and wet conditioning benefits, compared toother asymmetric dialkyl quaternized ammonium salt cationic surfactantssuch as those having a longer branched alkyl group and a shorterstraight alkyl group together with two more C1-4 alkyl groups.Furthermore, it has been found that; among the above asymmetric dialkylquaternized ammonium salt cationic surfactants having a longer straightsaturated alkyl group and a shorter branched alkyl group, those havingthe shorter branched alkyl of in one embodiment from 6 to 10 carbonatoms, in another embodiment 8 carbon atoms provide further improvedbalance between ease-to-rinse feel and wet conditioning benefits,compared to those having the shorter branched alkyl of more than 11carbon atoms.

It is believed that the use of alkylsulfate such as methosulfate andethosulfate as a salt-forming anion may be able to provide betterconditioning benefits especially wet conditioning benefits, compared toother salt-forming anions.

Nonlimiting examples of asymmetric dialkyl quaternized ammonium saltcationic surfactants useful herein include: stearyl ethylhexyl dimoniummethosulfate available, for example, with tradename Arquad HTL8-MS fromAkzo Nobel having the following structure:

B. Styling Agents

The dissolvable personal care solids of the present invention maycomprise an active agent comprising one or more styling agents suitablefor application to the hair. Many such styling polymers are known in theart, including dispersible and water-insoluble organic polymers andwater-insoluble silicone-grafted polymers. Such polymers can be made byconventional or otherwise known polymerization techniques well known inthe art, an example of which includes free radical polymerization.Examples of dispersible polymers are disclosed in, for example, U.S.Pat. No. 5,391,368. Examples of latex polymers are disclosed in, forexample, U.S. Pat. No. 4,710,374.

The hair styling polymers suitable for use in the shampoo composition ofthe present invention include organic hair styling polymers well knownin the art. The organic styling polymers may be homopolymers,copolymers, terpolymers or other higher polymers, but must comprise oneor more polymerizable hydrophobic monomers to thus render the resultingstyling polymer hydrophobic and water-insoluble as defined herein. Thestyling polymers may therefore further comprise other water soluble,hydrophillic monomers provided that the resulting styling polymers havethe requisite hydrophobicity and water insolubility.

As used herein, the term “hydrophobic monomer” refers to polymerizableorganic monomers that can form with like monomers a water-insolublehomopolymer, and the term “hydrophilic monomer” refers to polymerizableorganic monomers that can form with like monomers a water-solublehomopolymer.

The organic styling polymers useful herein have a weight averagemolecular weight of at least about 20,000, in one embodiment greaterthan about 25,000, in another embodiment greater than about 30,000, inyet another embodiment greater than about 35,000. There is no upperlimit for molecular weight except that which limits applicability of theinvention for practical reasons, such as processing, aestheticcharacteristics, formulateability, etc. In general, the weight averagemolecular weight will be less than about 10,000,000, more generally lessthan about 5,000,000, and typically less than about 2,000,000. In oneembodiment, the weight average molecular weight will be between about20,000 and about 2,000,000, in another embodiment between about 30,000and about 1,000,000, and in yet another embodiment between about 40,000and about 500,000.

The organic styling polymers also in one embodiment have a glasstransition temperature (Tg) or crystalline melting point (Tm) of atleast about −20° C., in another embodiment from about 20° C. to about80° C., in yet another embodiment from about 20° C. to about 60° C.Styling polymers having these Tg or Tm values form styling films on hairthat are not unduly sticky or tacky to the touch. As used herein, theabbreviation “Tg” refers to the glass transition temperature of thebackbone of the polymer, and the abbreviation “Tm” refers to thecrystalline melting point of the backbone, if such a transition existsfor a given polymer. In one embodiment, both the Tg and the Tm, if any,are within the ranges recited hereinabove.

The organic styling polymers are carbon chains derived frompolymerization of hydrophobic monomers such as ethylenically unsaturatedmonomers, cellulosic chains or other carbohydrate-derived polymericchains. The backbone may comprise ether groups, ester groups, amidegroups, urethanes, combinations thereof, and the like.

The organic styling polymers may further comprise one or morehydrophilic monomers in combination with the hydrophobic monomersdescribed herein, provided that the resulting styling polymer has therequisite hydrophobic character and water-insolubility. Suitablehydrophilic monomers include, but are not limited to, acrylic acid,methacrylic acid, N,N-dimethylacrylamide, dimethyl aminoethylmethacrylate, quaternized dimethylaminoethyl methacrylate,methacrylamide, N-t-butyl acrylamide, maleic acid, maleic anhydride andits half esters, crotonic acid, itaconic acid, acrylamide, acrylatealcohols, hydroxyethyl methacrylate, diallyldimethyl ammonium chloride,vinyl ethers (such as methyl vinyl ether), maleimides, vinyl pyridine,vinyl imidazole, other polar vinyl heterocyclics, styrene sulfonate,allyl alcohol, vinyl alcohol (such as that produced by the hydrolysis ofvinyl acetate after polymerization), salts of any acids and amineslisted above, and mixtures thereof. Hydrophillic monomers useful hereininclude acrylic acid, N,N-dimethyl acrylamide, dimethylaminoethylmethacrylate, quaternized dimethyl aminoethyl methacrylate, vinylpyrrolidone, salts of acids and amines listed above, and combinationsthereof.

Suitable hydrophobic monomers for use in the organic styling polymerinclude, but are not limited to, acrylic or methacrylic acid esters ofC1-C18 alcohols, such as methanol, ethanol, methoxy ethanol, 1-propanol,2-propanol, 1-butanol, 2-methyl-1-propanol, 1-pentanol, 2-pentanol,3-pentanol, 2-methyl-1-butanol, 1-methyl-1-butanol, 3-methyl-1-butanol,1-methyl-1-pentanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol,t-butanol(2-methyl-2-propanol), cyclohexanol, neodecanol,2-ethyl-1-butanol, 3-heptanol, benzyl alcohol, 2-octanol,6-methyl-1-heptanol, 2-ethyl-1-hexanol, 3,5-dimethyl-1-hexanol,3,5,5-trimethyl-1-hexanol, 1-decanol, 1-dodecanol, 1-hexadecanol, 1-octadecanol, and the like, the alcohols having in one embodiment from about1 to about 18 carbon atoms, in another embodiment from about 1 to about12 carbon atoms; styrene; polystyrene macromer; vinyl acetate; vinylchloride; vinylidene chloride; vinyl propionate; alpha-methylstyrene;t-butylstyrene; butadiene; cyclohexadiene; ethylene; propylene; vinyltoluene; and mixtures thereof. Hydrophobic monomers useful hereininclude n-butyl methacrylate, isobutyl methacrylate, t-butyl acrylate,t-butyl methacrylate, 2-ethylhexyl methacrylate, methyl methacrylate,vinyl acetate, and mixtures thereof, in one embodiment t-butyl acrylate,t-butyl methacrylate, or combinations thereof. Surprisingly, it has beenfound that conventional styling polymers consisting of copolymers ofvinyl pyrrolidone and vinyl acetate do not exhibit the curl retentionbenefits required of the present invention.

The styling polymers for use in the shampoo composition in oneembodiment comprise from about 20% to 100%, in another embodiment fromabout 50% to about 100%, in yet another embodiment from about 60% toabout 100%, by weight of the hydrophobic monomers, and may furthercomprise from zero to about 80% by weight of hydrophilic monomers. Theparticular selection and combination of monomers for incorporation intothe styling polymer will help determine its formulational properties. Byappropriate selection and combination of, for example, hydrophilic andhydrophobic monomers, the styling polymer can be optimized for physicaland chemical compatibility with the selected styling polymer solventdescribed hereinafter and other components of the shampoo composition.The selected monomer composition of the organic styling polymer must,however, render the styling polymer water-insoluble but soluble in theselected styling polymer solvent described hereinafter. In this context,the organic styling polymer is soluble in the styling polymer solvent ifthe organic polymer is solubilized in the solvent at 25° C. at thepolymer and solvent concentrations of the shampoo formulation selected.However, a solution of the organic styling polymer and styling polymersolvent may be heated to speed up solubility of the styling polymer inthe styling polymer solvent. Such styling polymer and solventformulation, including the selection of monomers for use in the stylingpolymer, to achieve the desired solubility is well within the skill ofone in the art.

Examples of organic styling polymers useful herein include t-butylacrylate/2-ethylhexyl acrylate copolymers having a weight/weight ratioof monomers of about 95/5, about 90/10, about 80/20, about 70/30, about60/40, and about 50/50; t-butyl acrylate/2-ethylhexyl methacrylatecopolymers having a weight/weight ratio of monomers of about 95/5, about90/10, about 80/20, about 70/30, about 60/40, and about 50/50; t-butylmethacrylate/2-ethylhexyl acrylate copolymers having a weight/weightratio of monomers of about 95/5, about 90/10, about 80/20, about 70/30,about 60/40, and about 50/50; t-butyl methacrylate/2-ethylhexylmethacrylate copolymers having a weight/weight ratio of monomers ofabout 95/5, about 90/10, about 80/20, about 70/30, about 60/40, andabout 50/50; t-butyl ethacrylate/2-ethylhexyl methacrylate copolymershaving a weight/weight ratio of monomers of about 95/5, about 90/10,about 80/20, about 70/30, about 60/40, and mixtures thereof.

Polymers useful herein are t-butyl acrylate/2-ethylhexyl methacrylatecopolymers having a weight/weight ratio of monomers of about 95/5, about90/10, about 80/20, about 70/30, about 60/40, and about 50/50; t-butylmethacrylate/2-ethylhexyl methacrylate copolymers having a weight/weightratio of monomers of about 95/5, about 90/10, about 80/20, about 70/30,about 60/40, and about 50/50; and mixtures thereof.

Examples of other suitable styling polymers are described in U.S. Pat.No. 4,272,511, to Papantoniou et al., issued Jun. 9, 1981; U.S. Pat. No.5,672,576, to Behrens et al., issued Sep. 30, 1997; and U.S. Pat. No.4,196,190, to Gehman et al., issued Apr. 1, 1980.

Other suitable styling polymers for use in the shampoo composition ofthe present invention are silicone-grafted hair styling resins. Thesepolymers may be used alone or in combination with the organic stylingpolymers described hereinbefore. Many such polymers suitable for use inthe shampoo composition herein are known in the art. These polymers arecharacterized by polysiloxane moieties covalently bonded to and pendantfrom an uncross-linked polymeric carbon-based backbone.

In one embodiment the backbone of the silicone-grafted polymer is acarbon chain derived from polymerization of ethylenically unsaturatedmonomers, but can also be cellulosic chains or othercarbohydrate-derived polymeric chains to which polysiloxane moieties arependant. The backbone can also include ether groups, ester groups, amidegroups, urethane groups and the like. The polysiloxane moieties can besubstituted on the polymer or can be made by co-polymerization ofpolysiloxane-containing polymerizable monomers (e.g. ethylenicallyunsaturated monomers, ethers, and/or epoxides) withnon-polysiloxane-containing polymerizable monomers. In one embodimentthe silicone-grafted styling polymers have a weight average molecularweight of at least about 10.000, in one embodiment greater than about20,000, in another embodiment greater than about 35,000, in yet anotherembodiment greater than about 50,000. In one embodiment the weightaverage molecular weight of the silicone-grafted styling polymer is lessthan 300,000, in another embodiment less than about 250,000, and in yetanother embodiment less than about 150,000.

The silicone-grafted styling polymers for use in the shampoo compositioncomprise “silicone-containing” (or “polysiloxane-containing”) monomers,which form the silicone macromer pendant from the backbone, andnon-silicone-containing monomers, which form the organic backbone of thepolymer.

In one embodiment the silicone-grafted polymers comprise an organicbackbone, in another embodiment a carbon backbone derived fromethylenically unsaturated monomers, such as a vinyl polymeric backbone,and a polysiloxane macromer (in yet another embodiment arepolydialkylsiloxane, in another embodiment polydimethylsiloxane) graftedto the backbone. As used hereinafter the term “PDMS” refers topolydimethylsiloxane. In one embodiment the polysiloxane macromer shouldhave a weight average molecular weight of at least about 500, in anotherembodiment from about 1,000 to about 100,000, in another embodiment fromabout 2,000 to about 50,000, and in yet another embodiment about 5,000to about 20,000. Organic backbones contemplated include those that arederived from polymerizable, ethylenically unsaturated monomers,including vinyl monomers, and other condensation monomers (e.g., thosethat polymerize to form polyamides and polyesters), ring-openingmonomers (e.g., ethyl oxazoline and caprolactone), etc. Alsocontemplated are backbones based on cellulosic chains, ether-containingbackbones, etc.

Suitable silicone grafted polymers for use in the shampoo compositioncomprise monomer units derived from: at least one free radicallypolymerizable ethylenically unsaturated monomer or monomers and at leastone free radically polymerizable polysiloxane-containing ethylenicallyunsaturated monomer or monomers.

The silicone grafted polymers suitable for use in the shampoocomposition generally comprise from about 1% to about 50%, by weight, ofpolysiloxane-containing monomer units and from about 50% to about 99% byweight, of non-polysiloxane-containing monomers. Thenon-polysiloxane-containing monomer units can be derived from thehydrophilic and/or hydrophobic monomer units described hereinbefore.

The styling polymer for use in the shampoo composition can thereforecomprise combinations of the hydrophobic and/or polysiloxane-containingmonomer units described herein, with or without hydrophilic comonomersas described herein, provided that the resulting styling polymer has therequisite characteristics as described herein.

Suitable polymerizable polysiloxane-containing monomers include, but arenot limited to, those monomers that conform to the formula:X(Y)_(n)Si(R)_((3−m))Z_(m)wherein X is an ethylenically unsaturated group copolymerizable with thehydrophobic monomers described herein, such as a vinyl group; Y is adivalent linking group; R is a hydrogen, hydroxyl, lower alkyl (e.g.C1-C4), aryl, alkaryl, alkoxy, or alkylamino; Z is a monovalent siloxanepolymeric moiety having a number average molecular weight of at leastabout 500, which is essentially unreactive under copolymerizationconditions, and is pendant from the vinyl polymeric backbone describedabove; n is 0 or 1; and m is an integer from 1 to 3. These polymerizablepolysiloxane-containing monomers have a weight average molecular weightas described above. Examples of such polysiloxane-containing monomerscan be found in U.S. Pat. No. 6,177,390B1.

Another polysiloxane monomer conforms to the following formula:X—CH₂—(CH₂)_(s)—Si(R1)_(3-m)—Z_(m)wherein: s is an integer from 0 to about 6, and in one embodiment is 0,1, or 2; m is an integer from 1 to 3, and in one embodiment is 1; R1 isC1-C10 alkyl or C7-C10 alkylaryl, in another embodiment C1-C6 alkyl orC7-C10 alkylaryl, in yet another embodiment C1-C2 alkyl; and X and Z areas defined above

The silicone grafted styling polymers suitable for use in the shampoocomposition in one embodiment comprise from about 50% to about 99%, inanother embodiment from about 60% to about 98%, in another embodimentfrom about 75% to about 95%, by weight of the polymer, of non-siliconemacromer-containing monomer units, e.g. the total hydrophobic andhydrophilic monomer units described herein, and in one embodiment fromabout 1% to about 50%, in another embodiment from about 2% to about 40%,in yet another embodiment from about 5% to about 25%, of siliconemacromer-containing monomer units, e.g. the polysiloxane-containingmonomer units described herein. The level of hydrophilic monomer unitscan be in one embodiment from about 0% to about 70%, in anotherembodiment from about 0% to about 50%, in another embodiment from about0% to about 30%, and in yet another embodiment from about 0% to about15%; the level of hydrophobic monomer units, can be in one embodimentfrom 30% to about 99%, in another embodiment from about 50% to about98%, in another embodiment from about 70% to about 95%, and in yetanother embodiment from about 85% to about 95%.

Examples of some suitable silicone grafted polymers for use in theshampoo composition herein are listed below. Each listed polymer isfollowed by its monomer composition as weight part of monomer used inthe synthesis:

-   (i)    t-butylacrylatye/t-butyl-methacrylate/2-ethylhexyl-methacrylate/PDMS    macromer-20,000 molecular weight macromer 31/27/32/10-   (ii) t-butylmethacrylate/2-ethylhexyl-methacrylate/PDMS    macromer-15,000 molecular weight macromer 75/10/15-   (iii) t-butylmethacrylate/2-ethylhexyl-acrylate/PDMS macromer-10,000    molecular weight macromer 65/15/20-   (iv) t-butylacrylate/2-ethylhexyl-acrylate/PDMS macromer-14,000    molecular weight macromer 77/11/12-   (v) t-butylacrylate/2-ethylhexyl-methacrylate/PDMS macromer-13,000    molecular weight macromer 81/9/10

Examples of other suitable silicone grafted polymers for use in theshampoo composition of the present invention are described in EPOApplication 90307528.1, published as EPO Application 0 408 311 A2 onJan. 11, 1991, Hayama, et al.; U.S. Pat. No. 5,061,481, issued Oct. 29,1991, Suzuki et al.; U.S. Pat. No. 5,106,609, Bolich et al., issued Apr.21, 1992; U.S. Pat. No. 5,100,658, Bolich et al., issued Mar. 31, 1992;U.S. Pat. No. 5,100,657, Ansher-Jackson, et al., issued Mar. 31, 1992;U.S. Pat. No. 5,104,646, Bolich et al., issued Apr. 14, 1992; U.S. Ser.No. 07/758,319, Bolich et al, filed Aug. 27, 1991, U.S. Ser. No.07/758,320, Torgerson et al., filed Aug. 27, 1991.

C. Anti-Dandruff Agents

(i). Pyrithione or a Polyvalent Metal Salt of Pyrithione

The present may comprise pyrithione or a polyvalent metal salt ofpyrithione. Any form of polyvalent metal pyrithione salts may be used,including platelet and needle structures. Salts for use herein includethose formed from the polyvalent metals magnesium, barium, bismuth,strontium, copper, zinc, cadmium, zirconium and mixtures thereof, and inone embodiment the salt is formed with zinc. In one embodiment the saltis zinc salt of 1-hydroxy-2-pyridinethione (known as “zinc pyrithione”or “ZPT”); ZPT in platelet particle form, wherein the particles have anaverage size of up to about 20 μm, in one embodiment up to about 5 μm,in another embodiment up to about 2.5 μm.

Pyridinethione anti-microbial and anti-dandruff agents are described,for example, in U.S. Pat. Nos. 2,809,971; 3,236,733; 3,753,196;3,761,418; 4,345,080; 4,323,683; 4,379,753; and 4,470,982.

Zinc pyrithione may be made by reacting 1-hydroxy-2-pyridinethione(i.e., pyrithione acid) or a soluble salt thereof with a zinc salt (e.g.zinc sulfate) to form a zinc pyrithione precipitate, as illustrated inU.S. Pat. No. 2,809,971.

The pyrithione or polyvalent metal salt of pyrithione can be from about0.01% to about 5%; and in one embodiment from about 0.1% to about 2%.

In embodiments having a particulate zinc material and a pyrithione orpolyvalent metal salt of pyrithione, the ratio of particulate zincmaterial to pyrithione or a polyvalent metal salt of pyrithione can befrom 5:100 to 10:1; and in another embodiment from about 2:10 to 5:1;and in yet another embodiment from 1:2 to 3:1.

(ii). Furametpyr

In one embodiment, the present invention may comprise furametpyr.Furametpyr is a fungicide, and more specifically, furametpyr is in thecarboxamide class of anti-fungals. While not being bound by theory, itis generally thought that the furametpyr mechanism is the inhibition ofmitochondrial succinate oxidation.

Embodiments of the present invention can include from about 0.01% toabout 3% of a furametpyr; in another embodiment from about 0.1% to about2%; in yet another embodiment from about 0.2% to about 1.5%.

In the present invention, the combination of furametpyr with pyrithioneor the polyvalent metal salts of pyrithione may result in an increase inefficacy of a composition. In an embodiment of the present invention,such an increase may be an increase in efficacy for anti-dandruff.

In a further embodiment of the present invention, furametpyr may also beused in combination with other anti-microbial agents. Non-limitingexamples of other anti-microbial agents are ketoconazole, climbazole,octopirox, salicylic acid, coal tar, selenium sulfide and mixturesthereof. Such combinations of furametpyr with other anti-microbialagents, may result in an increase in efficacy of a composition, and evenmore particularly, may increase anti-dandruff efficacy.

Furametpyr generally can be represented by the following formula I:

-   -   Formula: C₁₇H₂₀Cl N₃O₂    -   CAS/Registry Number: 123572-88-3    -   CA Index Name: 1H-Pyrazole-4-carboxamide,        5-chloro-N-(1,3-dihydro-1,1,3-trimethyl-4-isobenzofuranyl)-1,3-dimethyl-(9CI)    -   Trade Names: Limber®

(iii). Particulate Zinc Material

In a further embodiment of the present invention, the composition of thepresent invention may include an effective amount of a particulate zincmaterial. Embodiments of the present invention can include from about0.001% to about 10% of a particulate zinc layered material; in anotherembodiment from about 0.01% to about 7%; in yet another embodiment fromabout 0.1% to about 5%.

Particulate zinc materials (PZM's) are zinc-containing materials whichremain mostly insoluble within formulated compositions. Many benefits ofPZM's require the zinc ion to be chemically available without beingsoluble, this is termed zinc lability. Physical properties of theparticulate material have the potential to impact lability. We havediscovered several factors which impact zinc lability and therefore haveled to development of more effective formulas based on PZM's.

Particle physical properties which have been found to be important tooptimize zinc lability of PZM's are morphology of the particle, surfacearea, crystallinity, bulk density, surface charge, refractive index, andpurity level and mixtures thereof. Control of these physical propertieshas been shown to increase product performance.

Examples of particulate zinc materials useful in certain embodiments ofthe present invention include the following:

Inorganic Materials: Zinc aluminate, Zinc carbonate, Zinc oxide andmaterials containing zinc oxide (i.e., calamine), Zinc phosphates (i.e.,orthophosphate and pyrophosphate), Zinc selenide, Zinc sulfide, Zincsilicates (i.e., ortho- and meta-zinc silicates), Zinc silicofluoride,Zinc Borate, Zinc hydroxide and hydroxy sulfate, zinc-containing layeredmaterials and combinations thereof.

Further, layered structures are those with crystal growth primarilyoccurring in two dimensions. It is conventional to describe layerstructures as not only those in which all the atoms are incorporated inwell-defined layers, but also those in which there are ions or moleculesbetween the layers, called gallery ions (A.F. Wells “StructuralInorganic Chemistry” Clarendon Press, 1975). Zinc-containing layeredmaterials (ZLM's) may have zinc incorporated in the layers and/or asmore labile components of the gallery ions.

Many ZLM's occur naturally as minerals. Common examples includehydrozincite (zinc carbonate hydroxide), basic zinc carbonate,aurichalcite (zinc copper carbonate hydroxide), rosasite (copper zinccarbonate hydroxide) and many related minerals that are zinc-containingNatural ZLM's can also occur wherein anionic layer species such asclay-type minerals (e.g., phyllosilicates) contain ion-exchanged zincgallery ions. All of these natural materials can also be obtainedsynthetically or formed in situ in a composition or during a productionprocess.

Another common class of ZLM's, which are often, but not always,synthetic, is layered doubly hydroxides, which are generally representedby the formula [M²⁺ _(1−x)M³⁺ _(x)(OH)₂]^(x+)A^(m−) _(x/m).nH₂O and someor all of the divalent ions (M²⁺) would be represented as zinc ions(Crepaldi, E L, Pava, P C, Tronto, J, Valim, J B J. Colloid Interfac.Sci. 2002, 248, 429-42).

Yet another class of ZLM's can be prepared called hydroxy double salts(Morioka, H., Tagaya, H., Karasu, M, Kadokawa, J, Chiba, K Inorg. Chem.1999, 38, 4211-6). Hydroxy double salts can be represented by thegeneral formula [M²⁺ _(1−x)M²⁺ _(1−x)(OH)_(3(1−y))]⁺A^(n−)_((1=3y)/n).nH₂O where the two metal ion may be different; if they arethe same and represented by zinc, the formula simplifies to[Zn_(1+x)(OH)₂]^(2x+)2xA⁻.nH₂O. This latter formula represents (wherex=0.4) common materials such as zinc hydroxychloride and zinchydroxynitrate. These are related to hydrozincite as well wherein thedivalent anion is replaced by a monovalent anion. These materials canalso be formed in situ in a composition or in or during a productionprocess.

These classes of ZLM's represent relatively common examples of thegeneral category and are not intended to be limiting as to the broaderscope of materials which fit this definition, including: Natural Zinccontaining materials/Ores and Minerals: Sphalerite (zinc blende),Wurtzite, Smithsonite, Franklinite, Zincite, Willemite, Troostite,Hemimorphite and combinations thereof. Organic Salts: Zinc fatty acidsalts (i.e., caproate, laurate, oleate, stearate, etc.), Zinc salts ofalkyl sulfonic acids, Zinc naphthenate, Zinc tartrate, Zinc tannate,Zinc phytate, Zinc monoglycerolate, Zinc allantoinate, Zinc urate, Zincamino acid salts (i.e., methionate, phenylalinate, tryptophanate,cysteinate, etc) and combinations thereof. Polymeric Salts: Zincpolycarboxylates (i.e., polyacrylate), Zinc polysulfate and combinationsthereof. Physically Adsorbed Forms: Zinc-loaded ion exchange resins,Zinc adsorbed on particle surfaces, Composite particles in which zincsalts are incorporated, (i.e., as core/shell or aggregate morphologies)and combinations thereof. Zinc Salts: zinc oxalate, zinc tannate, zinctartrate, zinc citrate, zinc oxide, zinc carbonate, zinc hydroxide, zincoleate, zinc phosphate, zinc silicate, zinc stearate, zinc sulfide, zincundecylate, and the like, and mixtures thereof; in one embodiment thezinc salt is zinc oxide or zinc carbonate basic.

Commercially available sources of zinc oxide include Z-Cote and Z-CoteHPI (BASF), and USP I and USP II (Zinc Corporation of America).

Commercially available sources of zinc carbonate include Zinc CarbonateBasic (Cater Chemicals: Bensenville, Ill., USA), Zinc Carbonate(Shepherd Chemicals: Norwood, Ohio, USA), Zinc Carbonate (CPS UnionCorp.: New York, N.Y., USA), Zinc Carbonate (Elementis Pigments: Durham,UK), and Zinc Carbonate AC (Bruggemann Chemical: Newtown Square, Pa.,USA).

Basic zinc carbonate, which also may be referred to commercially as“Zinc Carbonate” or “Zinc Carbonate Basic” or “Zinc Hydroxy Carbonate”,is a synthetic version consisting of materials similar to naturallyoccurring hydrozincite. The idealized stoichiometry is represented byZn₅(OH)₆(CO₃)₂ but the actual stoichiometric ratios can vary slightlyand other impurities may be incorporated in the crystal lattice.

Surfactants

The surfactant component of the dissolvable porous solid is essential asa processing aide in preparing a stable solid porous structure for thedissolvable porous solids described herein, although it is understoodthat the surfactant component should not generate substantial latherduring consumer usage for the non-lathering porous solids of the presentinvention. Accordingly, the surfactant component is employed primarilyas a process aid in making a stable foam, wherein the surfactantincludes conventional surfactants or emulsifiers that need not provideany lathering performance. Examples of emulsifiers for use as asurfactant component herein include mono- and di-glycerides, fattyalcohols, polyglycerol esters, propylene glycol esters, sorbitan estersand other emulsifiers known or otherwise commonly used to stabilized airinterfaces, as for example those used during preparation of aeratedfoodstuffs such as cakes and other baked goods and confectionaryproducts, or the stabilization of cosmetics such as hair mousses.

(i) Ionic Surfactants

The dissolvable personal care solids of the present invention maycomprise a maximum level of 10% (or less than 10%) of ionic surfactantsto be used primarily as a process aid in making a stable foam solid, soas to preclude substantial lather formation during consumer usage anddissolution of the porous solid. Ionic surfactants suitable for use inthe dissolvable porous solids of the present invention include anionicsurfactants, cationic surfactants, zwitterionic surfactants, amphotericsurfactants, or combinations thereof.

Anionic surfactants suitable for use in the personal care compositionsof the present invention include those described in McCutcheon'sDetergents and Emulsifiers, North American Edition (1986), AlluredPublishing Corp.; McCutcheon's, Functional Materials, North AmericanEdition (1992), Allured Publishing Corp.; and U.S. Pat. No. 3,929,678(Laughlin et al.).

Non-limiting examples of anionic surfactants suitable for use hereininclude alkyl and alkyl ether sulfates, sulfated monoglycerides,sulfonated olefins, alkyl aryl sulfonates, primary or secondary alkanesulfonates, alkyl sulfosuccinates, acyl taurates, acyl isethionates,alkyl glycerylether sulfonate, sulfonated methyl esters, sulfonatedfatty acids, alkyl phosphates, acyl glutamates, acyl sarcosinates, alkylsulfoacetates, acylated peptides, alkyl ether carboxylates, acyllactylates, anionic fluorosurfactants, sodium lauroyl glutamate, andcombinations thereof.

Anionic surfactants suitable for use in the personal care compositionsof the present invention include alkyl and alkyl ether sulfates. Thesematerials have the respective formulae ROSO₃M and RO(C₂H₄O)_(x)SO₃M,wherein R is alkyl or alkenyl of from about 8 to about 24 carbon atoms,x is 1 to 10, and M is a water-soluble cation such as ammonium, sodium,potas-sium and triethanolamine. The alkyl ether sulfates are typicallymade as condensation products of ethylene oxide and monohydric alcohol'shaving from about 8 to about 24 carbon atoms. In one embodiment, R hasfrom about 10 to about 18 carbon atoms in both the alkyl and alkyl ethersulfates. The alcohol's can be derived from fats, e.g., coconut oil ortallow, or can be synthetic. Lauryl alcohol and straight chain alcohol'sderived from coconut oil are can be useful herein. Such alcohol's arereacted with about 1 to about 10, and in one embodiment 3 to about 5,molar proportions of ethylene oxide and the resulting mixture ofmolecular species having, for ex-ample, an average of 3 moles ofethylene oxide per mole of alcohol, is sulfated and neutralized.

Specific examples of alkyl ether sulfates which may be used in thepersonal care compositions are sodium and ammonium salts of coconutalkyl triethylene glycol ether sulfate; tallow alkyl triethylene glycolether sulfate, and tallow alkyl hexaoxyethylene sulfate. Alkyl ethersulfates useful herein are those comprising a mixture of individualcompounds, said mixture having an average alkyl chain length of fromabout 10 to about 16 carbon atoms and an average degree of ethoxylationof from about 1 to about 4 moles of ethylene oxide.

Other suitable anionic surfactants include water-soluble salts of theorganic, sulfuric acid reaction products of the general formula[R¹—SO₃-M], wherein R¹ is chosen from the group consisting of a straightor branched chain, saturated aliphatic hydrocarbon radical having fromabout 8 to about 24, and in one embodiment about 10 to about 18, carbonatoms; and M is a cation. Important examples are the salts of an organicsulfuric acid reaction product of a hydrocarbon of the methane series,including iso-, neo-, ineso-, and n-paraffins, having about 8 to about24 carbon atoms, and in one embodiment about 10 to about 18 carbon atomsand a sulfonating agent, e.g., SO₃, H₂SO₄, oleum, obtained according toknown sulfonation methods, including bleaching and hydrolysis. Anionicsurfactants useful herein include alkali metal and ammonium sulfonatedC₁₀₋₁₈ n-paraffins.

Additional examples of suitable anionic surfactants are the reactionproducts of fatty acids esterified with isethionic acid and neutralizedwith sodium hydroxide where, for example, the fatty acids are derivedfrom coconut oil; sodium or potassium salts of fatty acid amides ofmethyl tauride in which the fatty acids, for example, are derived fromcoconut oil. Other suitable anionic surfactants of this variety aredescribed in U.S. Pat. Nos. 2,486,921, 2,486,922 and 2,396,278.

Still other suitable anionic surfactants are the succinamates, examplesof which include disodium N-octadecylsulfosuccinamate; diammoniumlaurylsulfosuccinamate; tetrasodiumN-(1,2-dicarboxyethyl)-N-octadecylsulfosuccinamate; diamyl ester ofsodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid;and dioctyl esters of sodium sulfosuccinic acid.

Other suitable anionic surfactants include olefin sulfonates havingabout 12 to about 24 carbon atoms. The term “olefin sulfonates” is usedherein to mean compounds which can be produced by the sulfonation ofa-olefins by means of uncomplexed sulfur trioxide, followed byneutralization of the acid reaction mixture in conditions such that anysulfones which have been formed in the reaction are hydrolyzed to givethe corresponding hydroxy-alkanesulfonates. The sulfur trioxide can beliquid or gaseous, and is usually, but not necessarily, diluted by inertdiluents, for example by liquid SO₂, chlorinated hydrocarbons, etc.,when used in the liquid form, or by air, nitrogen, gaseous SO₂, etc.,when used in the gaseous form.

The α-olefins from which the olefin sulfonates are derived aremono-olefins having about 12 to about 24 carbon atoms, and in oneembodiment about 14 to about 16 carbon atoms. In one embodiment, theyare straight chain olefins.

In addition to the true alkene sulfonates and a proportion ofhydroxy-alkanesulfonates, the olefin sulfonates can contain minoramounts of other materials, such as alkene disulfonates depending uponthe reaction conditions, proportion of reactants, the nature of thestarting olefins and impurities in the olefin stock and side reactionsduring the sulfonation process.

Another class of anionic surfactants suitable for use in the personalcare compositions are the b-alkyloxy alkane sulfonates. These compoundshave the following formula:

where R₁ is a straight chain alkyl group having from about 6 to about 20carbon atoms, R₂ is a lower alkyl group having from about 1 to about 3carbon atoms, and M is a water-soluble cation as hereinbefore described.

Other suitable surfactants are described in McCutcheon's, Emulsifiersand Detergents, 1989 Annual, published by M. C. Publishing Co., and inU.S. Pat. No. 3,929,678.

Anionic surfactants for use in the personal care compositions includeammonium lauryl sulfate, ammonium laureth sulfate, triethylamine laurylsulfate, triethylamine laureth sulfate, triethanolamine lauryl sulfate,triethanolamine laureth sulfate, monoethanolamine lauryl sulfate,monoethanolamine laureth sulfate, diethanolamine lauryl sulfate,diethanolamine laureth sulfate, lauric monoglyceride sodium sulfate,sodium lauryl sulfate, sodium laureth sulfate, potassium lauryl sulfate,potassium laureth sulfate, sodium lauryl sarcosinate, sodium lauroylsarcosinate, lauryl sarcosine, cocoyl sarcosine, ammonium cocoylsulfate, ammonium lauroyl sulfate, sodium cocoyl sulfate, sodium lauroylsulfate, potassium cocoyl sulfate, potassium lauryl sulfate,triethanolamine lauryl sulfate, triethanolamine lauryl sulfate,monoethanolamine cocoyl sulfate, monoethanolamine lauryl sulfate, sodiumtridecyl benzene sulfonate, sodium dodecyl benzene sulfonate, andcombinations thereof.

Amphoteric surfactants suitable for use in the personal carecompositions of the present invention includes those that are broadlydescribed as derivatives of aliphatic secondary and tertiary amines inwhich the aliphatic radical can be straight or branched chain andwherein one of the aliphatic substituents contains from about 8 to about18 carbon atoms and one contains an anionic water solubilizing group,e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. Examplesof compounds falling within this definition are sodium3-dodecyl-aminopropionate, sodium 3-dodecylaminopropane sulfonate,sodium lauryl sarcosinate, N-alkyltaurines such as the one prepared byreacting dodecylamine with sodium isethionate according to the teachingof U.S. Pat. No. 2,658,072, N-higher alkyl aspartic acids such as thoseproduced according to the teaching of U.S. Pat. No. 2,438,091, and theproducts described in U.S. Pat. No. 2,528,378. Zwitterionic surfactantssuitable for use include those that are broadly described as derivativesof aliphatic quaternary ammonium, phosphonium, and sulfonium compounds,in which the aliphatic radicals can be straight or branched chain, andwherein one of the aliphatic substituents contains from about 8 to about18 carbon atoms and one contains an anionic group, e.g., carboxy,sulfonate, sulfate, phosphate, or phosphonate. Zwitterionic surfactantssuitable for use in the multiphase, personal care composition includebetaines, including cocoamidopropyl betaine.

The amphoteric surfactants of the present invention may also includealkylamphoacetates including lauroamphoacetate and cocoamphoacetate.Alkylamphoacetates can be comprised of monoacetates and diacetates. Insome types of alkylamphoacetates, diacetates are impurities orunintended reaction products.

Zwitterionic surfactants suitable for use in the personal carecompositions of the present invention include those that are broadlydescribed as derivatives of aliphatic quaternary ammonium, phosphonium,and sulfonium compounds, in which the aliphatic radicals can be straightor branched chain, and wherein one of the aliphatic substituentscontains from about 8 to about 18 carbon atoms and one contains ananionic group, e.g., carboxy, sulfonate, sulfate, phosphate, orphosphonate. Such suitable zwitterionic surfactants can be representedby the formula:

wherein R² contains an alkyl, alkenyl, or hydroxy alkyl radical of fromabout 8 to about 18 carbon atoms, from 0 to about 10 ethylene oxidemoieties and from 0 to about 1 glyceryl moiety; Y is selected from thegroup consisting of nitrogen, phosphorus, and sulfur atoms; R³ is analkyl or monohydroxyalkyl group containing about 1 to about 3 carbonatoms; X is 1 when Y is a sulfur atom, and 2 when Y is a nitrogen orphosphorus atom; R⁴ is an alkylene or hydroxyalkylene of from about 1 toabout 4 carbon atoms and Z is a radical selected from the groupconsisting of carboxylate, sulfonate, sulfate, phosphonate, andphosphate groups.

Other zwitterionic surfactants suitable for use herein include betaines,including high alkyl betaines such as coco dimethyl carboxymethylbetaine, cocoamidopropyl betaine, cocobetaine, lauryl amidopropylbetaine, oleyl betaine, lauryl dimethyl carboxymethyl betaine, lauryldimethyl alphacarboxyethyl betaine, cetyl dimethyl carboxymethylbetaine, lauryl bis-(2-hydroxyethyl) carboxymethyl betaine, stearylbis-(2-hydroxypropyl) carboxymethyl betaine, oleyl dimethylgamma-carboxypropyl betaine, and laurylbis-(2-hydroxypropyl)alpha-carboxyethyl betaine. The sulfobetaines maybe represented by coco dimethyl sulfopropyl betaine, stearyl dimethylsulfopropyl betaine, lauryl dimethyl sulfoethyl betaine, laurylbis-(2-hydroxyethyl) sulfopropyl betaine and the like; amidobetaines andamidosulfobetaines, wherein the RCONH(CH₂)₃ radical is attached to thenitrogen atom of the betaine are also useful in this invention.

(ii) Non-Ionic Surfactants

In one embodiment non-ionic surfactants are surfactants to be employedas a process aid in making a the dissolvable porous solids of thepresent invention. Suitable nonionic surfactants for use in the presentinvention include those described in McCutcheion's Detergents andEmulsifiers, North American edition (1986), Allured Publishing Corp.,and McCutcheion's Functional Materials, North American edition (1992).Suitable nonionic surfactants for use in the personal care compositionsof the present invention include, but are not limited to,polyoxyethylenated alkyl phenols, polyoxyethylenated alcohols,polyoxyethylenated polyoxypropylene glycols, glyceryl esters of alkanoicacids, polyglyceryl esters of alkanoic acids, propylene glycol esters ofalkanoic acids, sorbitol esters of alkanoic acids, polyoxyethylenatedsorbitor esters of alkanoic acids, polyoxyethylene glycol esters ofalkanoic acids, polyoxyethylenated alkanoic acids, alkanolamides,N-alkylpyrrolidones, alkyl glycosides, alkyl polyglucosides, alkylamineoxides, and polyoxyethylenated silicones.

Representative polyoxyethylenated alcohols include alkyl chains rangingin the C9-C16 range and having from about 1 to about 110 alkoxy groupsincluding, but not limited to, laureth-3, laureth-23, ceteth-10,steareth-10, steareth-100, beheneth-10, and commercially available fromShell Chemicals, Houston, Tex. under the trade names Neodol® 91, Neodol®23, Neodol® 25, Neodol® 45, Neodol® 135, Neodol® 67, Neodol® PC 100,Neodol® PC 200, Neodol® PC 600, and mixtures thereof.

Also available commercially are the polyoxyethylene fatty ethersavailable commercially under the Brij® trade name from Uniqema,Wilmington, Del., including, but not limited to, Brij® 30, Brij® 35,Brij® 52, Brij® 56, Brij® 58, Brij® 72, Brij® 76, Brij® 78, Brij® 93,Brij® 97, Brij® 98, Brij® 721 and mixtures thereof.

Suitable alkyl glycosides and alkyl polyglucosides can be represented bythe formula (S)n—O—R wherein S is a sugar moiety such as glucose,fructose, mannose, galactose, and the like; n is an integer of fromabout 1 to about 1000, and R is a C8-C30 alkyl group. Examples of longchain alcohols from which the alkyl group can be derived include decylalcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearylalcohol, oleyl alcohol, and the like. Examples of these surfactantsinclude alkyl polyglucosides wherein S is a glucose moiety, R is a C8-20alkyl group, and n is an integer of from about 1 to about 9.Commercially available examples of these surfactants include decylpolyglucoside and lauryl polyglucoside available under trade names APG®325 CS, APG® 600 CS and APG® 625 CS) from Cognis, Ambler, Pa. Alsouseful herein are sucrose ester surfactants such as sucrose cocoate andsucrose laurate and alkyl polyglucosides available under trade namesTriton™ BG-10 and Triton™ CG-110 from The Dow Chemical Company, Houston,Tx.

Other nonionic surfactants suitable for use in the present invention areglyceryl esters and polyglyceryl esters, including but not limited to,glyceryl monoesters, glyceryl monoesters of C12-22 saturated,unsaturated and branched chain fatty acids such as glyceryl oleate,glyceryl monostearate, glyceryl monopalmitate, glyceryl monobehenate,and mixtures thereof, and polyglyceryl esters of C12-22 saturated,unsaturated and branched chain fatty acids, such as polyglyceryl-4isostearate, polyglyceryl-3 oleate, polyglyceryl-2-sesquioleate,triglyceryl diisostearate, diglyceryl monooleate, tetraglycerylmonooleate, and mixtures thereof.

Also useful herein as nonionic surfactants are sorbitan esters. Sorbitanesters of C12-22 saturated, unsaturated, and branched chain fatty acidsare useful herein. These sorbitan esters usually comprise mixtures ofmono-, di-, tri-, etc. esters. Representative examples of suitablesorbitan esters include sorbitan monolaurate (SPAN® 20), sorbitanmonopalmitate (SPAN® 40), sorbitan monostearate (SPAN® 60), sorbitantristearate (SPAN® 65), sorbitan monooleate (SPAN® 80), sorbitantrioleate (SPAN® 85), and sorbitan isostearate.

Also suitable for use herein are alkoxylated derivatives of sorbitanesters including, but not limited to, polyoxyethylene (20) sorbitanmonolaurate (Tween® 20), polyoxyethylene (20) sorbitan monopalmitate(Tween® 40), polyoxyethylene (20) sorbitan monostearate (Tween® 60),polyoxyethylene (20) sorbitan monooleate (Tween® 80), polyoxyethylene(4) sorbitan monolaurate (Tween® 21), polyoxyethylene (4) sorbitanmonostearate (Tween® 61), polyoxyethylene (5) sorbitan monooleate(Tween® 81), and mixtures thereof, all available from Uniqema.

Also suitable for use herein are alkylphenol ethoxylates including, butnot limited to, nonylphenol ethoxylates (Tergitol™ NP-4, NP-6, NP-7,NP-8, NP-9, NP-10, NP-11, NP-12, NP-13, NP-15, NP-30, NP-40, NP-50,NP-55, NP-70 available from The Dow Chemical Company, Houston, Tx.) andoctylphenol ethoxylates (Triton™ X-15, X-35, X-45, X-114, X-100, X-102,X-165, X-305, X-405, X-705 available from The Dow Chemical Company,Houston, Tex).

Also suitable for use herein are alkanolamides including cocamidemonoethanolamine (CMEA) and tertiary alkylamine oxides includinglauramine oxide and cocamine oxide.

Nonionic surfactants useful herein have an HLB (hydrophile-lipophilebalance) of at least 8, in one embodiment greater than 10, and inanother embodiment greater than 12. The HLB represents the balancebetween the hydrophilic and lipophilic moieties in a surfactant moleculeand is commonly used as a method of classification. The HLB values forcommonly-used surfactants are readily available in the literature (e.g.,HLB Index in McCutcheon's Emulsifiers and Detergents, MC Publishing Co.,2004).

(iii) Polymeric Surfactants

Polymeric surfactants can also be surfactants to be employed as aprocess aid in making the dissolvable porous solids of the presentinvention, either alone or in combination with ionic and/or nonionicsurfactants. Suitable polymeric surfactants for use in the personal carecompositions of the present invention include, but are not limited to,block copolymers of ethylene oxide and fatty alkyl residues, blockcopolymers of ethylene oxide and propylene oxide, hydrophobicallymodified polyacrylates, hydrophobically modified celluloses, siliconepolyethers, silicone copolyol esters, diquaternarypolydimethylsiloxanes, and co-modified amino/polyether silicones.

Suitable silicone polyethers, co-modified amino/polyether silicones andsilicone copolyol esters may include rake-type copolymers, ABAcopolymers, trisiloxane surfactants, and mixtures thereof. Suitableexamples include, but are not limited to, polyoxyethylenateddimethicones (KF-607, KF-351, KF-352, KF-353, KF-354L, KF-355A, KF-615A,KF-945, KF-618, KF-6011, KF-6015 from Shin-Etsu, Japan) including PEG-10Dimethicone (KF-6017 from Shin-Etsu, Japan), polyoxyethylenated andpolypropoxylenated dimethicones (Abil EM 90 and Abil EM97 from Evonik,Germany, SF1528 and products available under the Silwet and Silsofttrade names from GE Silicones, New York, and DC 5225C Formulation Aidfrom Dow Corning, Mich.), co-modified amino/polyether silicones(X-22-3939A, X-22-3908A from Shin-Etsu, Japan), silicone copolyol estersinclude, but are not limited to, Dimethicone PEG-7 isostearate (UltrasilDW18 from Noveon) and Dimethicone PEG-7 olivate (Ultrasil DW-O).

Suitable copolymers of ethylene oxide and fatty alkyl residues includenonionic polyoxyethylene compounds having fatty (hydrophobic) residuesat the distill ends of each polyoxyethylene chain including, but notlimited to, PEG-150 distearate, PEG-30 Dipolyhydroxystearate (ArlacelP135 from Uniqem), and PEG-12 dipolyhydroxysterate (Arlacel P114).

Suitable diquaternary polydimethylsiloxanes have an average molecularweight in the range from 1000 to 4000, and may contain siloxane chainsin the range from 5 to 40 dimethylsiloxy units. Such a diquaternarypolydimethylsiloxane is available from Goldschmidt AG, Essen, Germany,as “ABIL-Quat” 3272. “ABIL-Quat” 3270 is another diquaternarypolydimethylsiloxane available from Goldschmidt.

Suitable hydrophobically modified polyacrylates are typified by thePemulen® products and have the INCI name of Acrylates C10-30 AlkylAcrylates Crosspolymer including, but not limited to Pemulen® TR1.

Suitable hydrophobically modified celluloses include alkyl modifiedhydroxyethyl cellulose including, but not limited to, Cetyl HydroxyethylCellulose (Natrosol® Plus CS)

Block copolymers of ethylene oxide and propylene oxide include thoserepresented by the following formula: HO(C2H4)x(C3H6O)y(C2H4)xH whereinvalues of x may range from about 10 to 110 and values y may range,independently of x, from about 20 to 60. Suitable examples are betterknown as poloxamer block copolymers (124, 188, 237, 338, 407) under thetrade name of Pluronic® (L44NF, F68NF, F87NF, F108NF, F127NF) from BASF,Germany.

Water-Soluble Polymer (“Polymer Structurant”)

The present invention comprises water-soluble polymer that functions asa structurant. As used herein, the term “water-soluble polymer” is broadenough to include both water-soluble and water-dispersible polymers, andis defined as a polymer with a solubility in water, measured at 25° C.,of at least about 0.1 gram/liter (g/L). In some embodiments, thepolymers have a solubility in water, measured at 25° C., of from about0.1 gram/liter (g/L) to about 500 grams/liter (g/L). (This indicatesproduction of a macroscopically isotropic or transparent, colored orcolorless solution). The polymers for making these solids may be ofsynthetic or natural origin and may be modified by means of chemicalreactions. They may or may not be film-forming. These polymers should bephysiologically acceptable, i.e., they should be compatible with theskin, mucous membranes, the hair and the scalp.

The terms “water-soluble polymer” and “polymer structurant” are usedinterchangeably herein. Furthermore, whenever the singular term“polymer” is stated, it should be understood that the term is broadenough to include one polymer or a mixture of more than one polymer. Forinstance, if a mixture of polymers is used, the polymer solubility asreferred to herein would refer to the solubility of the mixture ofpolymers, rather than to the solubility of each polymer individually.

The one or more water-soluble polymers of the present invention areselected such that their weighted average molecular weight is from about40,000 to about 500,000, in one embodiment from about 50,000 to about400,000, in yet another embodiment from about 60,000 to about 300,000,and in still another embodiment from about 70,000 to about 200,000. Theweighted average molecular weight is computed by summing the averagemolecular weights of each polymer raw material multiplied by theirrespective relative weight percentages by weight of the total weight ofpolymers present within the porous solid.

The water-soluble polymer(s) of the present invention can include, butare not limited to, synthetic polymers including polyvinyl alcohols,polyvinylpyrrolidones, polyalkylene oxides, polyacrylates, caprolactams,polymethacrylates, polymethylmethacrylates, polyacrylamides,polymethylacrylamides, polydimethylacrylamides, polyethylene glycolmonomethacrylates, polyurethanes, polycarboxylic acids, polyvinylacetates, polyesters, polyamides, polyamines, polyethyleneimines,maleic/(acrylate or methacrylate) copolymers, copolymers of methylvinylether and of maleic anhydride, copolymers of vinyl acetate and crotonicacid, copolymers of vinylpyrrolidone and of vinyl acetate, copolymers ofvinylpyrrolidone and of caprolactam, vinyl pyrollidone/vinyl acetatecopolymers, copolymers of anionic, cationic and amphoteric monomers, andcombinations thereof.

The water-soluble polymer(s) of the present invention may also beselected from naturally sourced polymers including those of plant originexamples of which include karaya gum, tragacanth gum, gum Arabic,acemannan, konjac mannan, acacia gum, gum ghatti, whey protein isolate,and soy protein isolate; seed extracts including guar gum, locust beangum, quince seed, and psyllium seed; seaweed extracts such asCarrageenan, alginates, and agar; fruit extracts (pectins); those ofmicrobial origin including xanthan gum, gellan gum, pullulan, hyaluronicacid, chondroitin sulfate, and dextran; and those of animal originincluding casein, gelatin, keratin, keratin hydrolysates, sulfonickeratins, albumin, collagen, glutelin, glucagons, gluten, zein, andshellac.

Modified natural polymers are also useful as water-soluble polymer(s) inthe present invention. Suitable modified natural polymers include, butare not limited to, cellulose derivatives such ashydroxypropylmethylcellulose, hydroxymethylcellulose,hydroxyethylcellulose, methylcellulose, hydroxypropylcellulose,ethylcellulose, carboxymethylcellulose, cellulose acetate phthalate,nitrocellulose and other cellulose ethers/esters; and guar derivativessuch as hydroxypropyl guar.

Water-soluble polymers of the present invention include polyvinylalcohols, polyvinylpyrrolidones, polyalkylene oxides, starch and starchderivatives, pullulan, gelatin, hydroxypropylmethylcelluloses,methycelluloses, and carboxymethycelluloses.

Water-soluble polymers of the present invention may also includepolyvinyl alcohols, and hydroxypropylmethylcelluloses. Suitablepolyvinyl alcohols include those available from Celanese Corporation(Dallas, Tex.) under the Celvol trade name including, but not limitedto, Celvol 523, Celvol 530, Celvol 540, Celvol 518, Celvol, 513, Celvol508, Celvol 504, and combinations thereof. Suitablehydroxypropylmethylcelluloses include those available from the DowChemical Company (Midland, Mich.) under the Methocel trade nameincluding, but not limited, to Methocel E50, Methocel E15, Methocel E6,Methocel E5, Methocel E3, Methocel F50, Methocel K100, Methocel K3,Methocel A400, and combinations thereof including combinations withabove mentioned hydroxypropylmethylcelluloses.

In a particular embodiment, the above mentioned water-soluble polymer(s)of the present invention may be blended with any single starch orcombination of starches as a filler material in such an amount as toreduce the overall level of water-soluble polymers required, so long asit helps provide the dissolvable porous solid with the requisitestructure and physical/chemical characteristics as described herein. Insuch instances, the combined weight percentage of the water-solublepolymer(s) and starch-based material generally ranges from about 10% toabout 40 wt %, in one embodiment from about 12 to about 30%, and in aparticular embodiment from about 15% to about 25% by weight relative tothe total weight of the porous solid. The weight ratio of thewater-soluble polymer(s) to the starch-based material can generallyrange from about 1:10 to about 10:1, in one embodiment from about 1:8 toabout 8:1, in still another embodiment from about 1:7 to about 7:1, andin yet another embodiment from about 6:1 to about 1:6.

Typical sources for starch-based materials of the present invention caninclude cereals, tubers, roots, legumes and fruits. Native sources caninclude corn, pea, potato, banana, barley, wheat, rice, sago, amaranth,tapioca, arrowroot, canna, sorghum, and waxy or high amylase varietiesthereof.

The starch-based materials of the present invention may also includenative starches that are modified using any modification known in theart, including physically modified starches examples of which includesheared starches or thermally-inhibited starches; chemically modifiedstarches including those which have been cross-linked, acetylated, andorganically esterified, hydroxyethylated, and hydroxypropylated,phosphorylated, and inorganically esterified, cationic, anionic,nonionic, amphoteric and zwitterionic, and succinate and substitutedsuccinate derivatives thereof; conversion products derived from any ofthe starches, including fluidity or thin-boiling starches prepared byoxidation, enzyme conversion, acid hydrolysis, heat or aciddextrinization, thermal and or sheared products may also be usefulherein; and pregelatinized starches which are known in the art.

Plasticizer

The porous dissolvable solids of the present invention comprise a watersoluble plasticizing agent suitable for use in personal carecompositions. Non-limiting examples of suitable plasticizing agentsinclude polyols, copolyols, polycarboxylic acids, polyesters anddimethicone copolyols. Examples of useful polyols include, but are notlimited to, glycerin, diglycerin, propylene glycol, ethylene glycol,butylene glycol, pentylene glycol, cyclohexane dimethanol, hexane diol,polyethylene glycol (200-600), sugar alcohols such as sorbitol, manitol,lactitol and other mono- and polyhydric low molecular weight alcohols(e.g., C2-C8 alcohols); mono di- and oligo-saccharides such as fructose,glucose, sucrose, maltose, lactose, and high fructose corn syrup solidsand ascorbic acid. Examples of polycarboxylic acids include, but are notlimited to citric acid, maleic acid, succinic acid, polyacrylic acid,and polymaleic acid. Examples of suitable polyesters include, but arenot limited to, glycerol triacetate, acetylated-monoglyceride, diethylphthalate, triethyl citrate, tributyl citrate, acetyl triethyl citrate,acetyl tributyl citrate. Examples of suitable dimethicone copolyolsinclude, but are not limited to, PEG-12 dimethicone, PEG/PPG-18/18dimethicone, and PPG-12 dimethicone. Other suitable plasticizers of thepresent invention include, but are not limited to, alkyl and allylphthalates; napthalates; lactates (e.g., sodium, ammonium and potassiumsalts); sorbeth-30; urea; lactic acid; sodium pyrrolidone carboxylicacid (PCA); sodium hyraluronate or hyaluronic acid; soluble collagen;modified protein; monosodium L-glutamate; alpha & beta hydroxyl acidssuch as glycolic acid, lactic acid, citric acid, maleic acid andsalicylic acid; glyceryl polymethacrylate; polymeric plasticizers suchas polyquaterniums; proteins and amino acids such as glutamic acid,aspartic acid, and lysine; hydrogen starch hydrolysates; other lowmolecular weight esters (e.g., esters of C2-C10 alcohols and acids); andany other water soluble plasticizer known to one skilled in the art ofthe foods and plastics industries; and mixtures thereof. In oneembodiment, the plasticizers include glycerin or propylene glycol andcombinations thereof. European Patent Number EP283165B1 discloses othersuitable plasticizers, including glycerol derivatives such aspropoxylated glycerol.

Optional Ingredients

The porous dissolvable solids of the present invention may furthercomprise other optional ingredients that are known for use or otherwiseuseful in personal care compositions, provided that such optionalmaterials are compatible with the selected essential materials describedherein, or do not otherwise unduly impair product performance.

Such optional ingredients are most typically those materials approvedfor use in cosmetics and that are described in reference books such asthe CTFA Cosmetic Ingredient Handbook, Second Edition, The Cosmetic,Toiletries, and Fragrance Association, Inc. 1988, 1992. Non limitingexamples of such optional ingredients include preservatives, thickeners,sensates, plant extracts, absorbent particles, adhesive particles, hairfixatives, fibers, reactive agents, acids, bases, enzymes, suspendingagents, pH modifiers, pigment particles, anti-microbial agents, lotionagents, co-solvents or other additional solvents, and similar othermaterials.

Other optional ingredients include organic solvents, especially watermiscible solvents and co-solvents useful as solublizing agents forpolymeric structurants and as drying accelerators. Non-limiting examplesof suitable solvents include alcohols, esters, ketones, aromatichydrocarbons, aliphatic hydrocarbons, ethers, and combinations thereof.In one embodiment the alcohols are monohydric. In another embodimentmonohydric alcohols are ethanol, iso-propanol, and n-propanol. In oneembodiment esters are ethyl acetate and butyl acetate. Othernon-limiting examples of suitable organic solvents are benzyl alcohol,amyl acetate, propyl acetate, acetone, heptane, iso-butyl acetate,iso-propyl acetate, toluene, methyl acetate, iso-butanol, n-amylalcohol, n-butyl alcohol, hexane, and methyl ethyl ketone. methanol,ethanol, n-propanol, isopropanol, n-butanol, isobutanol,methylethylketone, acetone, and combinations thereof.

Other optional ingredients include latex or emulsion polymers,thickeners such as water soluble polymers, clays, silicas, waxes,ethylene glycol distearate, deposition aids, including coacervateforming components and quaternary amine compounds.

Product Form

The dissolvable porous solids of the present invention can be producedin any of a variety of product forms, including dissolvable poroussolids used alone or in combination with other personal care components.The dissolvable porous solids can be continuous or discontinuous whenused in the personal care compositions. Regardless of the product form,the key to all of the product form embodiments contemplated within thescope of the method of the present invention is the selected and defineddissolvable porous solid that comprises a combination of a solidpolymeric structurant and a surfactant-containing active ingredient, allas defined herein.

The dissolvable porous solids of the present invention are in the formof one or more flat sheets or pads of an adequate size to be able to behandled easily by the user. It may have a square, rectangle or discshape or any other shape. The pads can also be in the form of acontinuous strip including delivered on a tape-like roll dispenser withindividual portions dispensed via perforations and or a cuttingmechanism. Alternatively, the dissolvable porous solids of the presentinvention are in the form of one or more cylindrical objects, sphericalobjects, tubular objects or any other shaped object. The dissolvableporous solids of the present invention can have a thickness (caliper) offrom about 0.5 mm to about 10 mm, in one embodiment from about 1 mm toabout 7 mm, and in still another embodiment from about 2 mm to about 6mm. In the case of cylindrical, spherical, or other objects with more ofa third dimension versus a pad or strip, the thickness is taken as themaximum distance of the shortest dimension, i.e., the diameter of asphere or cylinder for instance.

The dissolvable porous solids of the present invention may comprise oneor more textured, dimpled or otherwise topographically patternedsurfaces including letters, logos or figures. The textured substrate canresult from the shape of the substrate, in that the outermost surface ofthe substrate contains portions that are raised with respect to otherareas of the surface. The raised portions can result from the formedshape of the article, for example the article can be formed originallyin a dimpled or waffle pattern. The raised portions can also be theresult of creping processes, imprinted coatings, embossing patterns,laminating to other layers having raised portions, or the result of thephysical form of the dissolvable porous solid substrate itself. Thetexturing can also be the result of laminating the substrate to a secondsubstrate that is textured.

In a particular embodiment, the dissolvable porous solids of the presentinvention can be perforated with holes or channels penetrating into orthrough the porous solid. These perforations can be formed during thedrying process via spikes extended from the surface of the underlyingmold, belt or other non-stick surface. Alternatively, these perforationscan be formed after the drying process via poking or sticking the poroussolids with pins, needles or other sharp objects. In one embodiment,these perforations are great in number per surface area, but not sogreat in number so as to sacrifice the integrity or physical appearanceof the porous solid. It has been found that such perforations increasethe dissolution rate of the porous solids into water relative toun-perforated porous solids.

The dissolvable porous solids of the present invention can also bedelivered via a water insoluble implement or device. For instance, theymay be attached or glued by some mechanism to an applicator tofacilitate application to hair and/or skin, i.e., a comb, wrag, wand, orany other conceivable water-insoluble applicator. Additionally, thedissolvable porous solids may be adsorbed to the surfaces of a separatehigh surface area water-insoluble implement, i.e., a porous sponge, apuff, a flat sheet etc. For the latter, the dissolvable porous solid ofthe present invention may be adsorbed as a thin film or layer orincluded within a specific regional space provided by the implement.

Product Types

Non-limiting examples of product type embodiments for use by thedissolvable porous solids and methods of the present invention includehair conditioning substrates, moisturizing substrates, other hairtreatment substrates, other skin or body treatment substrates, shavingpreparation substrates, pet care substrates, personal care substratescontaining pharmaceutical or other skin care active, moisturizingsubstrates, sunscreen substrates, chronic skin benefit agent substrates(e.g., vitamin-containing substrates, alpha-hydroxy acid-containingsubstrates, etc.), deodorizing substrates, fragrance-containingsubstrates, and the like.

II. METHOD OF MANUFACTURE

The personal care dissolvable porous solids of the present invention canbe prepared by the process comprising: (1) Preparing a processingmixture comprising surfactant(s), dissolved polymer structurant,plasticizer and other optional ingredients; (2) Aerating the mixture byintroducing a gas into the mixture; (3) Forming the aerated wet mixtureinto a desired one or more shapes; and (4) Drying the aerated wetmixture to a desired final moisture content (e.g., from about 0.5 to 15%moisture, by addition of energy).

Preparation of Processing Mixture

The processing mixture is generally prepared by dissolving the polymerstructurant in the presence of water, plasticizer and other optionalingredients by heating followed by optional cooling. This can beaccomplished by any suitable heated batch agitation system or via anysuitable continuous system involving either single screw or twin screwextrusion or heat exchangers together with either high shear or staticmixing. Any process can be envisioned such that the polymer isultimately dissolved in the presence of water, the surfactant(s), theplasticizer, and other optional ingredients including step-wiseprocessing via pre-mix portions of any combination of ingredients.

The processing mixtures of the present invention comprise: from about15% to about 50% solids, in one embodiment from about 20% to about 40%solids, and in another embodiment from about 25% to about 35% solids, byweight of the processing mixture before drying; and have a viscosity offrom about 2,500 cps to about 35,000 cps, in one embodiment from about5,000 cps to about 30,000 cps, in another embodiment from about 7,500cps to about 25,000 cps, and in still another embodiment from about10,000 cps to about 20,000 cps. The processing mixture viscosity valuescan be measured on a suitable rheometer, such as a TA Instruments AR500Rheometer with 4.0 cm diameter parallel plate and 1,200 micron gap at ashear rate of 1.0 reciprocal seconds for a period of 30 seconds at 25°C. (available from TA Instruments, New Castle, Del.), or on a standardviscometer, such as a Brookfield Model DV-1 PRIME Digital Viscometerwith CP-41 and CP-42 spindles at a shear rate of 1.0 reciprocal secondsfor a period of 2 minutes at 25° C. (available from BrookfieldEngineering Laboratories, Inc., Middleboro, Mass.). The % solids contentis the summation of the weight percentages by weight of the totalprocessing mixture of all of the solid, semi-solid and liquid componentsexcluding water and any obviously volatile materials such as low boilingalcohols.

Aeration of Processing Mixture

The aeration of the processing mixture is accomplished by introducing agas into the mixture, in one embodiment by mechanical mixing energy butalso may be achieved via other physical or chemical means. The aerationmay be accomplished by any suitable mechanical processing means,including but not limited to: (i) Batch tank aeration via mechanicalmixing including planetary mixers or other suitable mixing vessels, (ii)semi-continuous or continuous aerators utilized in the food industry(pressurized and non-pressurized), (iii) gas injection, (iv) gasevolution via a pressure drop, or (v) spray-drying the processingmixture in order to form aerated beads or particles that can becompressed such as in a mould with heat in order to form the poroussolid.

In a particular embodiment, it has been discovered that the dissolvableporous solids of the present invention can be prepared withinsemi-continuous and continuous pressurized aerators that areconventionally utilized within the foods industry in the production ofmarshmallows. Suitable pressurized aerators include the Morton whisk(Morton Machine Co., Motherwell, Scotland), the Oakes continuousautomatic mixer (E. T. Oakes Corporation, Hauppauge, N.Y.), the FedcoContinuous Mixer (The Peerless Group, Sidney, Ohio), and the Preswhip(Hosokawa Micron Group, Osaka, Japan).

Forming the Aerated Wet Processing Mixture

The forming of the aerated wet processing mixture may be accomplished byany suitable means to form the mixture in a desired shape or shapesincluding, but not limited to (i) depositing the aerated mixture tospecially designed moulds comprising a non-interacting and non-sticksurface including Teflon, metal, HDPE, polycarbonate, neoprene, rubber,LDPE, glass and the like; (ii) depositing the aerated mixture intocavities imprinted in dry granular starch contained in a shallow tray(Starch moulding forming technique widely utilized in the confectioneryindustry); or (iii) depositing the aerated mixture onto a continuousbelt or screen comprising any non-interacting or non-stick materialTeflon, metal, HDPE, polycarbonate, neoprene, rubber, LDPE, glass andthe like which may be later stamped, cut, embossed or stored on a roll.

Drying the Formed Aerated Wet Processing Mixture

The drying of the formed aerated wet processing mixture may beaccomplished by any suitable means including, but not limited to: (i)drying room(s) including rooms with controlled temperature and pressureor atmospheric conditions; (ii) ovens including non-convection orconvection ovens with controlled temperature and optionally humidity;(iii) Truck/Tray driers, (iv) multi-stage inline driers; (v) impingementovens; (vi) rotary ovens/driers; (vii) inline roasters; (viii) rapidhigh heat transfer ovens and driers; (ix) dual plenum roasters, (x)conveyor driers, (xi) microwave drying technology, and combinationsthereof. Any suitable drying means that does not comprise freeze-dryingcan be used.

Optional ingredients may be imparted during any of the above describedfour processing steps or even after the drying process.

The dissolvable porous solids of the present invention may also beprepared with chemical foaming agents by in-situ gas formation (viachemical reaction of one or more ingredients, including formation of CO₂by an effervescent system).

III. PERFORMANCE AND PHYSICAL CHARACTERISTICS Dissolution Rate

The dissolvable porous solid of present invention has a Dissolution Ratethat allows the porous solid to rapidly disintegrate during use with theapplication with water. The Dissolution Rate of the dissolvable poroussolid component is determined in accordance with the methodologydescribed below.

Hand Dissolution Method: Approximately 0.5 g of the dissolvable poroussolid is placed in the palm of the hand while wearing nitrile gloves.7.5 cm³ of luke warm tap water (from about 30° C. to about 35° C.) isquickly applied to the product via syringe. Using a circular motion,palms of hands are rubbed together 2 strokes at a time until dissolutionoccurs (up to 30 strokes). The hand dissolution value is reported as thenumber of strokes it takes for complete dissolution or as 30 strokes asthe maximum (in the case for where the solid is considerednon-dissolving).

The dissolvable porous solids of the present invention have a handdissolution value of from about 1 to about 30 strokes, in one embodimentfrom about 2 to about 25 strokes, in another embodiment from about 3 toabout 20 strokes, and in still another embodiment from about 4 to about15 strokes.

Thickness

In one embodiment the dissolvable porous solid of present invention is aflat, flexible substrate in the form of a pad, a strip or tape andhaving a thickness of from about 0.5 mm to about 10 mm, in oneembodiment from about 1 mm to about 7 mm, and in another embodiment fromabout 2 mm to about 6 mm, as measured by the below methodology. In thecase of cylindrical, spherical, or other objects with more of a thirddimension versus a pad or strip, the thickness is taken as the maximumdistance of the shortest dimension, i.e., the diameter of a sphere orcylinder for instance, and the thickness ranges are the same asdescribed above.

The thickness of the dissolvable porous solid (i.e., substrate or samplesubstrate) is obtained using a micrometer or thickness gage, such as theMitutoyo Corporation Digital Disk Stand Micrometer Model NumberIDS-1012E (Mitutoyo Corporation, 965 Corporate Blvd, Aurora, Ill., USA60504). The micrometer has a 1 inch diameter platen weighing about 32grams, which measures thickness at an application pressure of about 40.7phi (6.32 gm/cm²).

The thickness of the dissolvable porous solid is measured by raising theplaten, placing a section of the sample substrate on the stand beneaththe platen, carefully lowering the platen to contact the samplesubstrate, releasing the platen, and measuring the thickness of thesample substrate in millimeters on the digital readout. The samplesubstrate should be fully extended to all edges of the platen to makesure thickness is measured at the lowest possible surface pressure,except for the case of more rigid substrates which are not flat. Formore rigid substrates which are not completely flat, a flat edge of thesubstrate is measured using only one portion of the platen impinging onthe flat portion of the substrate.

Basis Weight

The dissolvable porous solid component of the personal care compositionof the present invention has a basis weight of from about 125 grams/m²to about 3,000 grams/m², in one embodiment from about 150 grams/m² toabout 1,200 grams/m², in another embodiment from about 200 grams/m² toabout 1,000 grams/m², and in still another embodiment from about 300grams/m² to about 800 grams/m².

The Basis Weight of the dissolvable porous solid component of thepersonal care composition herein is calculated as the weight of thedissolvable porous solid component per area of the selected dissolvableporous solid (grams/m²). The area is calculated as the projected areaonto a flat surface perpendicular to the outer edges of the poroussolid. For a flat object, the area is thus computed based on the areaenclosed within the outer perimeter of the sample. For a sphericalobject, the area is thus computed based on the average diameter as3.14×(diameter/2)². For a cylindrical object, the area is thus computedbased on the average diameter and average length as diameter×length. Foran irregularly shaped three dimensional object, the area is computedbased on the side with the largest outer dimensions projected onto aflat surface oriented perpendicularly to this side. This can beaccomplished by carefully tracing the outer dimensions of the objectonto a piece of graph paper with a pencil and then computing the area byapproximate counting of the squares and multiplying by the known area ofthe squares or by taking a picture of the traced area (which canbeshaded-in for contrast) including a scale and using image analysistechniques.

Density

The dissolvable porous solid of the personal care compositions describedherein can be characterized in terms of a density determination.

The density of the dissolvable porous solid is determined by theequation: Calculated Density=Basis Weight of porous solid/(Porous SolidThickness×1,000), wherein the porous solid has a density of from about0.03 g/cm³ to about 0.4 g/cm³, in one embodiment from about 0.05 g/cm³to about 0.3 g/cm³, and in another embodiment from about 0.075 g/cm³ toabout 0.2 g/cm³. The Basis Weight and Thickness of the dissolvableporous solid are determined in accordance with the methodologiesdescribed herein.

Cell Inter-Connectivity

The dissolvable porous solid personal care products of the presentinvention with the above mentioned characteristics have a high degree ofcell inter-connectivity, i.e., are predominantly open-celled solid foamsas opposed to being predominantly closed-cell solid foams. The cellinter-connectivity can be assessed by cutting a 2-3 mm wide sliver ofthe solid in the z-direction using scissors or a sharp blade, measuredacross the normal x-y largest surface of the solid, and turning theresulting sliver by 90 degrees to reveal the internal cellular structureof the freshly cut cross-sectional area. This cross-sectional area canbe assessed by close visual inspection or, more accurately, by employingmagnification under a stereo microscope such as the SZX12 Stereomicroscope available from Olympus Olympus America Inc., Center Valley,Pa. The open-celled dissolvable porous solids of the present inventioncan easily be identified by examining the inner portion of thecross-sectional area which will comprise a predominantly threedimensional network of struts with open void spaces surrounding thestruts that are inter-connected to one another including in the thirddimension through the depth of the cross-section. In contrast, the innercross-section of a closed-cell foam will appear as discrete bubbles thatare cut across and then only being inter-connected at thecross-sectional surface in two dimensions by virtue of the cuttingprocess employed to generate the exposed cross-sectional area.

Solid Flexibility and Cohesiveness

The physical integrity of the dissolvable porous solids of the presentinvention (or solid cohesiveness) is assessed via a qualitative ratingsystem by two separate qualitative ratings (1 to 4 scale) onbrittleness/flexibility (brittle is breakable) and cohesiveness (ease inremoving from molds):

Brittleness/Flexibility Qualitative Rating Very Somewhat Somewhat Verybrittle = 1 brittle = 2 flexible = 3 flexible = 4

Cohesiveness Qualitative Rating (Ease of removal from molds) VerySomewhat Somewhat Very difficult = 1 difficult = 2 easy = 3 easy = 4These ratings are assessed on three dimensional molds and resulting flatsolids with z-dimension thicknesses between 3 mm and 10 mm and extendingin the x-y dimensions encompassing surface areas of between 10 cm² and60 cm² (with any x-y shape including circles, ovals, squares, rectanglesetc.). The examples herein were evaluated employing circular Teflonmolds and resulting removed solids with 4.15 cm diameters and depths of0.7 cm. The brittleness/flexibility rating is judged by bending the padin half and assessing each pad on its propensity for breakage/creasingversus the pads resiliency and ability to return to the original shape.The cohesiveness rating is judged by peeling a freshly dried (after atleast 20 hours at 40 degrees Celsius) solid from the mold and noting thedifficulty of removal. Solids with low cohesiveness ratings aredifficult to remove from the molds in one piece with significantadhesion to the mold surface and with significant solid remainingadhered to the mold after the solid removal process. Solids with highcohesiveness ratings are easy to peel from the molds in one piece andwithout significant solid remaining adhered to the mold after the solidremoval process.

Lather Volume Method

The dissolvable porous solid personal care compositions of the presentinvention can be considered substantially non-lathering with very lowlather volumes, which in one embodiment is from about 0 ml to about 20ml, in another embodiment is from about 0 ml to about 15 ml, and in yetanother embodiment is from about 0 ml to about 10 ml. For perspective,lathering personal care compositions (i.e., shampoos) typically generatelather volumes from about 70 ml to about 110 ml.

The lather volume assessment is performed on 15 g/10″ flat Orientalvirgin hair switches that have been treated with 0.098 g of artificialliquid sebum [10-22% olive oil, 18-20% coconut 6% dodecane, 1-4% stearicacid, 1-4% cholesterol, 1-4% coconut fatty acid, 18-20% choleth-24]. Thehair switch is rinsed with 9-11 grain, 100° F. water at 1.5 gallons/minfor 20 seconds with a shower nozzle. For testing the liquid controlproducts, 0.75 cm³ of liquid product are applied to the center of theswitch, the lower portion of hair on the switch is then rubbed over theproduct on the hair 10 times in a circular motion, followed by 40strokes back and forth (a total of 80 strokes). Lather speed is recordedas the number of strokes when the first lather is obviously generatedduring the 80 strokes. Lather from operator's gloves is transferred to agraduated cylinder with a 3.5 cm inside diameter and with totalcapacities of either 70 ml, 110 ml, or 140 ml depending on the totalamount of lather generated (height modification of standard sizedgraduated cylinders via a glass shop). Lather from hair is gatheredusing one downward stroke on the switch with a tight grip and is alsoplaced into the cylinder. Total lather volume is recorded inmilliliters. Three runs per test sample are performed and the mean ofthe three values is calculated. When testing the dissolvable poroussolids of the present invention, 0.20+/−0.01 grams of product areweighed with the aid of scissors if required and applied to the switchand then 2 cm3 of additional water are added to the product via syringe.The lathering technique is then performed as described for liquidproducts after a 10 second waiting time. If undissolved material remainsin hair, it is removed and the weight is determined when dry.

IV. METHODS OF USE

The compositions of the present invention may be used for treatingmammalian keratinous tissue such as hair and/or skin, and provide rapidrinse-ability. The method for conditioning the hair may comprise thesteps of: a) applying an effective amount of the dissolvable poroussolid to the hand, b) wetting the dissolvable porous solid with waterand rubbing to dissolve the solid, c) applying the dissolved material toeither the hair or skin such as to treat, and d) rinsing the dilutedtreatment from the hair or skin using water. These steps can be repeatedas many times as desired to achieve the desired treatment benefit.

According to yet another embodiment, a method is provided for providinga benefit to mammalian keratinous tissue, comprising the step ofapplying a composition according to the first embodiment to keratinoustissue in need of regulating.

The present invention provides for a method for regulating the conditionof mammalian keratinous tissue, comprising the step of applying one ormore compositions described herein to mammalian keratinous tissue inneed of regulation.

The amount of the composition applied, the frequency of application andthe period of use will vary widely depending upon the purpose ofapplication, the level of components of a given composition and thelevel of regulation desired. For example, when the composition isapplied for whole body or hair treatment, effective amounts generallyrange from about 0.3 grams to about 10 grams, in one embodiment fromabout 0.4 grams to about 5 grams, and in yet another embodiment fromabout 0.5 grams to about 3 grams.

V. Article of Commerce

The present invention provides for an article of commerce comprising oneor more compositions described herein, and a communication directing aconsumer to dissolve the porous solid and apply the dissolved mixture tokeratinous tissue to produce a treatment effect or benefit to keratinoustissue such as skin and/or hair. The communication may be printedmaterial attached directly or indirectly to packaging that contains thecomposition. Alternatively, the communication may be an electronic or abroadcast message that is associated with the article of manufacture.Alternatively, the communication may describe at least one possible use,capability, distinguishing feature and/or property of the article ofmanufacture.

VI. EXAMPLES

The following examples further describe and demonstrate embodimentswithin the scope of the present invention. The examples are given solelyfor the purpose of illustration and are not to be construed aslimitations of the present invention, as many variations thereof arepossible without departing from the spirit and scope of the invention.All exemplified amounts are concentrations by weight of the totalcomposition, i.e., wt/wt percentages, unless otherwise specified.

Example 1 Polyvinyl Alcohol and Glycerin Pre-Mix

The following polymer premix compositions were prepared for use duringthe preparation of the dissolvable porous solids of the presentinvention:

Component 1A 1B Distilled water 78.0 70.7 Glycerin 2.0 7.3 Polyvinylalcohol^(a) 20.0 22.0 Total 100.0 100.0 ^(a)87-89% hydrolyzed, MW 85,000to 124,000 available from Sigma Aldrich (Catalog Number 363081, batch09501BE)

Into an appropriately sized and cleaned vessel, the distilled water andglycerin is added with stirring at 100-300 rpm. The polyvinyl alcohol isweighed into a suitable container and slowly added to the main mixturein small increments using a spatula while continuing to stir whileavoiding the formation of visible lumps. The mixing speed is adjusted tominimize foam formation. The mixture is slowly heated to 85 C whilecontinuing to stir and then allowed to cool to room temperature. Thehazy mixture is allowed to sit overnight resulting in an amber coloredclear solution.

Example 2 Retail Liquid Hair Conditioner Product (Pantene Pro-V)

A liquid hair conditioner was purchased for use during the preparationof the dissolvable porous solids of the present invention. The productwas Pantene Pro-V Always Smooth Conditioner, 750 ml, which wasdistributed by Procter and Gamble, Cincinnati, Ohio. The product waspurchased in January 2008 with a lot number 71505395BC. The listedingredients on the bottle were: water, stearyl alcohol,cyclopentasiloxane, cetyl alcohol, stearamidopropyl dimethylamine,glutamic acid, dimethicone, panthenol, panthenyl ethyl ether, benzylalcohol, fragrance, EDTA, methylchloroisothiazolinone,methylisothiazolinone.

Example 3 Retail Liquid Hair Conditioner Product (Matrix Biolage)

A liquid hair conditioner was purchased for use during the preparationof the dissolvable porous solids of the present invention. The productwas Matrix Biolage Detangling Solution, 33.8 Fl. Oz., which wasdistributed by Matrix LLC, New York, N.Y. The product was purchased inFebruary 2008 with a lot number GC048. The listed ingredients on thebottle were: water, cetearyl alcohol, behentrimonium methosulfate, cetylalcohol, cyclopentasiloxane, behentrimonium chloride, phenoxyethanol,methylparaben, amodimethicone, fragrance, dimethiconol, stearamineoxide, propylene glycol, C11-15 pareth-7, C12-16 pareth-9, glycerin,trideceth-12, polysorbate 20, citric acid, sunflower extract, bitteralmond kernel oil, wheat germ extract, hops extract, ext. violet 2,pollen extract, blue 1.

Example 4 Non-Lathering Fast Dissolving Porous Solid Conditioner

The following dissolving porous solid is prepared in accordance to thepresent invention:

Component Wt % Polyvinyl alcohol premix from Example 1 40.0 Glycerin 1.2Retail Conditioner (Pantene Pro-V) from Example 2 51.8 Tween-60^(a) 7.0Total 100.0 ^(a)Available from Sigma, catalog number P1629, batch No.057K0115

The above composition is prepared by mixing via a SpeedMixer™ DAC 400 FVavailable from FlackTek, Inc., Landrum, S.C. 250 grams of the abovecomponents in the given amounts are added into a Max 300 SpeedMixer™plastic jar with all components being at room temperature. The mixtureis thoroughly mixed within the SpeedMixer™ which is run at a rage ofapproximately 2,750 rounds per minute for a time period of at least 30seconds. Approximately 20 grams of this mixture is reserved forviscosity measurements. The viscosity of the mixture is approximately7,000 to 9,000 cps at 1 s⁻¹.

The remainder of the above mixture is transferred into a 5 quartstainless steel bowl of a KitchenAid® Mixer Model K5SS (available fromHobart Corporation, Troy, Ohio) and fitted with a flat beaterattachment. The mixture is vigorously aerated at high speed forapproximately 3 minutes. The resulting aerated mixture is then spreadevenly with a spatula into circular Teflon molds (using rubber spatulasstraight edge to scrape off excess foam leaving a flat smooth surfacelevel with the top of the mold) with a 4.15 cm diameter and a depth of0.7 cm which are weighed before and after with average wet mixtureweights of 2.6+/−0.04 grams indicating an average wet foam density ofapproximately 0.28 grams/cm³.

The segregated molds are then placed into a 75 C convection oven for 30minutes and then placed into a 40 C convection oven for dryingovernight. The following day, the molds containing the dried mixture areweighed with subtraction of the original mold weights indicating dryweights of 0.60+/−0.02 grams. The resulting porous solids are removedfrom the molds with the aid of a thin spatula and tweezers and thethicknesses are measured with a caliper giving 5.0+/−0.4 mm indicatingan average resulting dry density of approximately 0.09 grams/cm³ andwith an average basis weight of 444 grams per square meter (GSM). Theresulting solids are determined (by the methodologies described herein):(i) to be predominantly open-celled; (ii) to exhibit good flexibilitywith a brittleness/flexibility qualitative rating of 3; (iii) to exhibitgood cohesiveness with cohesiveness qualitative rating of 3.5; (iv) tohave a rapid dissolution rate with a hand dissolution value of only 3strokes; (v) to provide good conditioning to hair; and (vi) to besubstantially non-lathering with a lather volume of less than 10 ml.

Comparative Example 5 Non-Lathering Slow Dissolving Porous SolidConditioner

The following dissolving porous solid is not prepared in accordance tothe present invention and included for comparative purposes to betterdemonstrate the important aspects of the present invention:

Component Wt % Polyvinyl alcohol premix from Example 1 60.0 RetailConditioner (Pantene Pro-V) from Example 2 40.0 Total 100.0

The above composition is prepared by mixing via a SpeedMixer™ DAC 400 FVavailable from FlackTek, Inc., Landrum, S.C. 110 grams of the abovecomponents in the given amounts are added into a Max 300 SpeedMixer™plastic jar with all components being at room temperature. The mixtureis thoroughly mixed within the SpeedMixer™ which is run at a rage ofapproximately 2,750 rounds per minute for a time period of at least 30seconds. Approximately 8 grams of this mixture is reserved for viscositymeasurements. The viscosity of the mixture is approximately 95,000 to140,000 cps at 1 s⁻¹.

The remainder of the above mixture is transferred into a 5 quartstainless steel bowl of a KitchenAid® Mixer Model K5SS (available fromHobart Corporation, Troy, Ohio) and fitted with a flat beaterattachment. The mixture is vigorously aerated at high speed forapproximately 4 minutes. The resulting aerated mixture is then spreadevenly with a spatula into circular Teflon molds (using rubber spatulasstraight edge to scrape off excess foam leaving a flat smooth surfacelevel with the top of the mold) with a 4.15 cm diameter and a depth of0.7 cm which are weighed before and after with average wet mixtureweights of 3.3+/−0.06 grams indicating an average wet foam density ofapproximately 0.35 grams/cm³.

The segregated molds are then placed into a 75 C convection oven for 30minutes and then placed into a 40 C convection oven for dryingovernight. The following day, the resulting porous solids are removedfrom the molds with the aid of a thin spatula and tweezers and theresulting solids are weighed indicating an average dry weight of0.69+/−0.08 grams. The thicknesses of the resulting solids are measuredwith a caliper giving 4.2+/−0 2 mm indicating an average resulting drydensity of approximately 0.12 grams/cm³ and with an average basis weightof 510 grams per square meter (GSM). The resulting solids are determined(by the methodologies described herein): (i) to be predominantlyclosed-celled; (ii) to exhibit poor flexibility with abrittleness/flexibility qualitative rating of 1; (iii) to exhibit poorcohesiveness with cohesiveness qualitative rating of 1.0; (iv) to benon-dissolving with a hand dissolution value of greater than 30 strokes;and (v) to deliver a poor in-use consumer experience (due to poordissolution resulting in un-dissolvable pieces).

Example 6 Non-Lathering Fast Dissolving Porous Solid Conditioner

The following dissolving porous solid is prepared in accordance to thepresent invention by dilution of the identical composition of Example 5.The viscosity of the mixture is approximately 95,000 to 140,000 cps at 1s⁻¹.

The viscosity of the mixture is lowered to within the limits of thepresent invention by dilution with de-ionized water. Approximately 90grams of de-ionized water are added to the mixture until the resultingviscosity reaches approximately 8,000 to 15,000 cps at 1 s⁻¹.

Approximately 100 grams of the reduced viscosity mixture is transferredinto a 5 quart stainless steel bowl of a KitchenAid® Mixer Model K5SS(available from Hobart Corporation, Troy, Ohio) and fitted with a flatbeater attachment. The mixture is vigorously aerated at high speed forapproximately 4 minutes. The resulting aerated mixture is then spreadevenly with a spatula into circular Teflon molds (using rubber spatulasstraight edge to scrape off excess foam leaving a flat smooth surfacelevel with the top of the mold) with a 4.15 cm diameter and a depth of0.7 cm which are weighed before and after with average wet mixtureweights of 2.3+/−0.03 grams indicating an average wet foam density ofapproximately 0.24 grams/cm³.

The segregated molds are then placed into a 75 C convection oven for 30minutes and then placed into a 40 C convection oven for dryingovernight. The following day, the molds containing the dried mixture areweighed with subtraction of the original mold weights indicating dryweights of 0.29+/−0.03 grams. The resulting porous solids are removedfrom the molds with the aid of a thin spatula and tweezers and thethicknesses are measured with a caliper giving 5.7+/−0.4 mm indicatingan average resulting dry density of approximately 0.04 grams/cm³ andwith an average basis weight of 214 grams per square meter (GSM). Theresulting solids are determined (by the methodologies described herein):(i) to be predominantly open-celled; (ii) to exhibit acceptableflexibility with a brittleness/flexibility qualitative rating of 2;(iii) to exhibit acceptable cohesiveness with cohesiveness qualitativerating of 2; (iv) to have a rapid dissolution rate with a handdissolution value of only 5 strokes; (v) to provide good conditioning tohair; and (vi) to be substantially non-lathering with a lather volume ofless than 10 ml.

Comparative Example 7 Non-Lathering Slow Dissolving Porous SolidConditioner

The following dissolving porous solid is not prepared in accordance tothe present invention and included for comparative purposes to betterdemonstrate the important aspects of the present invention. A mixturecomposition is prepared with a viscosity greater than Example 6, butless than Comparative Example 5:

Component Wt % Polyvinyl alcohol premix from Example 1 28.0 RetailConditioner (Pantene Pro-V) from Example 2 42.0 De-ionized Water 30.0Total 100.0

The above composition is prepared by mixing via a SpeedMixer™ DAC 400 FVavailable from FlackTek, Inc., Landrum, S.C. 110 grams of the abovecomponents in the given amounts are added into a Max 300 SpeedMixer™plastic jar with all components being at room temperature. The mixtureis thoroughly mixed within the SpeedMixer™ which is run at a rage ofapproximately 2,750 rounds per minute for a time period of at least 30seconds. Approximately 8 grams of this mixture is reserved for viscositymeasurements. The viscosity of the mixture is approximately 30,000 to35,000 cps at 1 s⁻¹.

The remainder of the above mixture is transferred into a 5 quartstainless steel bowl of a KitchenAid® Mixer Model K5SS (available fromHobart Corporation, Troy, Ohio) and fitted with a flat beaterattachment. The mixture is vigorously aerated at high speed forapproximately 8 minutes. The resulting aerated mixture is then spreadevenly with a spatula into circular Teflon molds (using rubber spatulasstraight edge to scrape off excess foam leaving a flat smooth surfacelevel with the top of the mold) with a 4.15 cm diameter and a depth of0.7 cm which are weighed before and after with average wet mixtureweights of 3.3+/−0.06 grams indicating an average wet foam density ofapproximately 0.33 grams/cm³.

The segregated molds are then placed into a 75 C convection oven for 30minutes and then placed into a 40 C convection oven to dry. After fivedays, the resulting porous solids are removed from the molds with theaid of a thin spatula and tweezers, but the foams were too crumbly toobtain accurate dry weights and densities. The resulting solids aredetermined (by the methodologies described herein): (i) to bepredominantly closed-celled; (ii) to exhibit poor flexibility with abrittleness/flexibility qualitative rating of 1.0; (iii) to exhibit poorcohesiveness with cohesiveness qualitative rating of 1.0; (iv) to benon-dissolving with a hand dissolution value of greater than 30 strokes;and (v) to deliver a poor in-use consumer experience (due to poordissolution resulting in un-dissolvable pieces).

Example 8 Non-Lathering Fast Dissolving Porous Solid Conditioner

The following dissolving porous solid is prepared in accordance to thepresent invention:

Component Wt % Polyvinyl alcohol premix from Example 1B 59.9 Glycerin1.2 Retail Conditioner (Matrix Biolage) from Example 3 18.6 Tween-60^(a)4.1 Distilled Water 17.4 Total 100.0 ^(a)Available from Sigma, catalognumber P1629, batch No. 057K0115

The above composition is prepared by mixing via a SpeedMixer™ DAC 400 FVavailable from FlackTek, Inc., Landrum, S.C. 125 grams of the abovecomponents in the given amounts are added into a Max 300 SpeedMixer™plastic jar with all components being at room temperature. The mixtureis thoroughly mixed within the SpeedMixer™ which is run at a rage ofapproximately 2,750 rounds per minute for a time period of at least 30seconds. Approximately 8 grams of this mixture is reserved for viscositymeasurements. The viscosity of the mixture is approximately 9,500 to10,500 cps at 1 s⁻¹.

Approximately 115 grams of the remainder of the above mixture istransferred into a 5 quart stainless steel bowl of a KitchenAid® MixerModel K5SS (available from Hobart Corporation, Troy, Ohio) and fittedwith a flat beater attachment. The mixture is vigorously aerated at highspeed for approximately 5 minutes. The resulting aerated mixture is thenspread evenly with a spatula into circular Teflon molds (using rubberspatulas straight edge to scrape off excess foam leaving a flat smoothsurface level with the top of the mold) with a 4.15 cm diameter and adepth of 0.7 cm which are weighed before and after with average wetmixture weights of 2.9+/−0.13 grams indicating an average wet foamdensity of approximately 0.31 grams/cm³.

The segregated molds are then placed into a 40 C convection oven fordrying overnight. The following day, the molds containing the driedmixture are weighed with subtraction of the original mold weightsindicating dry weights of 0.71+/−0.03 grams. The resulting porous solidsare removed from the molds with the aid of a thin spatula and tweezersand the thicknesses are measured with a caliper giving 5.1+/−0.1 mmindicating an average resulting dry density of approximately 0.10grams/cm³ and with an average basis weight of 525 grams per square meter(GSM). The resulting solids are determined (by the methodologiesdescribed herein): (i) to be predominantly open-celled; (ii) to exhibitgood flexibility with a brittleness/flexibility qualitative rating of4.0; (iii) to exhibit good cohesiveness with cohesiveness qualitativerating of 4.0; (iv) to have a rapid dissolution rate with a handdissolution value of only 8 strokes; (v) to provide good conditioning tohair; and (vi) to be substantially non-lathering with a lather volume ofless than 10 ml.

Discussion of Examples

The above representative examples are intended to demonstrate the keyaspects of the present invention. Example 4 is in accordance with thepresent invention and produced from a processing mixture comprisingpolyvinyl alcohol, a retail conditioner (Pantene Pro-V), a non-ionicsurfactant, and a viscosity of between 7,000 to 9,000 cps at 1 s⁻¹.Accordingly, Example 4 results in predominantly open-celled poroussolids with fast dissolution, good flexibility, good cohesiveness andwhile being substantially non-lathering. Comparative Example 5 is not inaccordance with the present invention and produced from a processingmixture comprising polyvinyl alcohol, a retail conditioner (PantenePro-V), but with a significantly higher viscosity of between 95,000 to140,000 cps at 1 s⁻¹. Accordingly, Comparative Example 5 results inpredominantly closed-celled porous solids that are non-dissolving aswell as having poor flexibility and poor cohesiveness. Example 6 is inaccordance with the present invention and produced from the identicalstarting processing mixture of Example 5, but the processing mixture isdiluted with water to enable a significantly lower viscosity of between8,000 to 15,000 cps at 1 s⁻¹. Accordingly, Example 6 results inpredominantly open-celled porous solids with fast dissolution as well asacceptable flexibility, acceptable cohesiveness and while beingsubstantially non-lathering. Comparative Example 7 is not in accordancewith the present invention and produced from a processing mixturecomprising polyvinyl alcohol, a retail conditioner (Pantene Pro-V), butwith a viscosity in-between that of Comparative Example 5 and Example 6of between 30,000 to 35,000 cps at 1 s⁻¹. Accordingly, ComparativeExample 7 results in predominantly closed-celled porous solids that arenon-dissolving as well as having poor flexibility and poor cohesiveness.Example 8 is in accordance with the present invention and produced froma processing mixture comprising polyvinyl alcohol, a retail conditioner(Matrix Biolage), a non-ionic surfactant, and a viscosity of between9,500 to 10,500 cps at 1 s⁻¹. Accordingly, Example 8 results inpredominantly open-celled porous solids with fast dissolution, goodflexibility, good cohesiveness and while being substantiallynon-lathering.

Collectively, the above examples demonstrate the discovery thatnon-lathering rapidly dissolving open-celled porous solids according tothe present invention can be produced provided that the processingmixture viscosity is within the desired range (or adjusted otherwise).Importantly, this discovery has surprisingly been found to hold trueindependent of the polymer mixture components (See Comparative Example 5relative to Example 6 which have the same composition and only differvia dilution of the original processing mixture) which goes against theconventionally accepted wisdom that it is the polymer type, andspecifically the molecular weight, that is the primary driver of poroussolid dissolution. Moreover, the above examples demonstrate thebeneficial effect of an added non-ionic surfactant on the structuralproperties of the fast dissolving open-celled porous solids (flexibilityand cohesiveness) while also not sacrificing the intended consumerperception of the solids being non-lathering during usage.

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm.”

Every document cited herein, including any cross referenced or relatedpatent or application, is hereby incorporated herein by reference in itsentirety unless expressly excluded or otherwise limited. The citation ofany document is not an admission that it is prior art with respect toany invention disclosed or claimed herein or that it alone, or in anycombination with any other reference or references, teaches, suggests ordiscloses any such invention. Further, to the extent that any meaning ordefinition of a term in this document conflicts with any meaning ordefinition of the same term in a document incorporated by reference, themeaning or definition assigned to that term in this document shallgovern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

What is claimed is:
 1. A process for forming a non-lathering personalcare article in the form of a porous dissolvable solid structure,wherein said process comprises the steps of: (a) preparing a pre-mixcomprising a substantially non-lathering surfactant, wherein thenon-lathering surfactant is selected from the group consisting ofnon-ionic surfactant, polymeric surfactant, and mixtures thereof,dissolved polymer structurant, an active selected from the groupconsisting of a conditioning agent, styling agent, anti-dandruff agentand combinations thereof and a plasticizer, wherein said pre-mix has:(i) from about 15% to 40% total solids; and (ii) a viscosity of fromabout 2,500 cps to 30,000 cps; (b) aerating said pre-mix by introducinga gas into the pre-mix to form a wet aerated pre-mix; (c) forming thewet aerated pre-mix into a desired one or more shapes to form shaped wetpre-mix; and (d) drying the shaped wet pre-mix to a desired finalmoisture content, wherein the final moisture content is from about 0.1%to about 15% moisture, to form the non-lathering personal care article,wherein said non-lathering personal care article has a density of fromabout 0.06 g/cm³ to about 0.15 g/cm³.
 2. The process of claim 1, whereinsaid water soluble polymer has a weighted average molecular weight offrom about 40,000 to about 500,000.
 3. The process of claim 1, whereinsaid process does not comprise a freeze-drying step.